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1. Hexanitrato complexes and hybrid double perovskites of Am3+ and Cm3+

Author: Michael L. Tarlton, Suntharalingam Skanthakumar, Valérie Vallet, Richard E. Wilson, Chemical Sciences and Engineering Division [Argonne], Physico-Chimie Moléculaire Théorique [PCMT], Argonne National Laboratory [Lemont] (ANL), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Ministry of Higher Education and Research, Hauts de France council and European Regional Development Fund (ERDF) through the Contrat de Projets État Region (CPER CLIMIBIO), HPC resources of CINES/IDRIS/TGCC under the allocation 2021–2022 (A0110801859) made by GENCI., DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences Geological and Biosciences Division, Heavy Element Chemistry program under Contract DE-AC02-06CH11357., ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Materials Chemistry, Metals and Alloys, Ceramics and Composites, General Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; The synthesis and structures of the homoleptic hexanitrato complexes of Am(III) and Cm(III), [(CH3)4N]2KAn(NO3)6 are reported. These compounds form a double perovskite structure type, A2B′BX6, crystallizing in the cubic space group Fm3m. Their electronic properties, as calculated using the Quantum Theory of Atoms in Molecules, are reported and compared to their lanthanide homologues Eu(III) and Gd(III).
Published: 2022

2. Influence of ice structure on the soft UV photochemistry of PAHs embedded in solid water

Author: J. Mascetti, Eric Michoulier, Jennifer A. Noble, C. Aupetit, Physique des interactions ioniques et moléculaires (PIIM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique [PCMT], Institut des Sciences Moléculaires [ISM], Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Centre National de la Recherche Scientifique (CNRS), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3)
Subjects: Astrochemistry, FOS: Physical sciences, methods: laboratory: molecular, Context (language use), 010402 general chemistry, Photochemistry, 01 natural sciences, Physics - Chemical Physics, 0103 physical sciences, Molecule, Reactivity (chemistry), Irradiation, Porosity, 010303 astronomy & astrophysics, Earth and Planetary Astrophysics (astro-ph.EP), Chemical Physics (physics.chem-ph), Physics, astrochemistry, Dangling bond, Astronomy and Astrophysics, ISM: molecules, 0104 chemical sciences, Amorphous solid, 13. Climate action, Space and Planetary Science, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], Astrophysics - Earth and Planetary Astrophysics
Abstract: The UV photoreactivity of polycyclic aromatic hydrocarbons (PAHs) in porous amorphous solid water has long been known to form both oxygenated photoproducts and photofragments. The aim of this study was to examine the influence of the ice structure upon reactivity under soft UV irradiation conditions. Mixtures of PAHs with amorphous solid water (porous and compact) and crystalline (cubic and hexagonal) ices were prepared in a high vacuum chamber and irradiated using a mercury lamp for up to 2.5 hours. The results show that the production of oxygenated PAHs is efficient only in amorphous water ice, while fragmentation can occur in both amorphous and crystalline ices. We conclude that the reactivity is driven by PAH-water interactions in favourable geometries, notably where dangling bonds are available at the surface of pores. These results suggest that the formation of oxygenated PAH molecules is most likely to occur in interstellar environments with porous (or compact) amorphous solid water and that this reactivity could considerably influence the inventory of aromatics in meteorites., Accepted for publication in A&A
Published: 2020

3. The DIRAC code for relativistic molecular calculations

Author: Joost N. P. van Stralen, Jon K. Laerdahl, Jógvan Magnus Haugaard Olsen, Hans Jørgen Aagaard Jensen, André Severo Pereira Gomes, Bruno Senjean, Ephraim Eliav, Marta L. Vidal, Stefan Knecht, Małgorzata Olejniczak, Erik D. Hedegård, Kenneth G. Dyall, Malaya K. Nayak, Radovan Bast, Miroslav Iliaš, Roberto Di Remigio, A. Sunaga, Ignacio Agustín Aucar, Elke Faßhauer, Benjamin Helmich-Paris, Trond Saue, Avijit Shee, Timo Fleig, Lucas Visscher, Markus Pernpointner, Christoph R. Jacob, Loïc Halbert, Groupe Méthodes et outils de la chimie quantique (LCPQ) (GMO), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry [Tromsø], University of Tromsø (UiT)-University of Tromsø (UiT), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Centre for Advanced Study at the Norwegian Academy of Science and Letters, The Norwegian Academy of Science and Letters, Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam [Amsterdam] (VU), Department of Chemistry and Pharmaceutical Sciences, Instituto de Modelado e Innovación Tecnológica (CONICET), Hylleraas Centre for Quantum Molecular Sciences (Hylleraas), Department of Chemistry [Oslo], Faculty of Mathematics and Natural Sciences [Oslo], University of Oslo (UiO)-University of Oslo (UiO)-Faculty of Mathematics and Natural Sciences [Oslo], University of Oslo (UiO)-University of Oslo (UiO), Dirac Solutions, School of Chemistry, Tel Aviv University [Tel Aviv], Department of Physics and Astronomy [Aarhus], Aarhus University [Aarhus], Division of Theoretical Chemistry, Max-Planck-Institut für Kohlenforschung (Coal Research), Max-Planck-Gesellschaft, Faculty of Natural Sciences, Matej Bel University (UMB), Institute of Physical and Theoretical Chemistry [Braunschweig], Technische Universität Braunschweig = Technical University of Braunschweig [Braunschweig], Laboratorium für Physikalische Chemie (ETH-LPC), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Department of Microbiology, Oslo University Hospital [Oslo], Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Technical University of Denmark [Lyngby] (DTU), Bhabha Atomic Research Centre (BARC), Government of India, Department of Atomic Energy, Centre of New Technologies, University of Warsaw (UW), Kybeidos GmbH, Instituut Lorentz (INSTITUUT LORENTZ), Universiteit Leiden [Leiden], Department of Chemistry [Michigan], Michigan State University [East Lansing], Michigan State University System-Michigan State University System, Department of Chemistry, Tokyo Metropolitan University, Tokyo Metropolitan University [Tokyo] (TMU), French Ministry of Higher Education and Research, region Hauts de France council, and the European Regional Development Fund (ERDF) project CPER CLIMIBIO, Slovak Research and Development Agency and the Scientific Grant Agency, APVV19-0164 and VEGA 1/0562/20, respectively., Financial support from the European Commission (MetEmbed, Project No. 745967) and the Villum Foundation (Young Investigator Program, Grant No. 29412), Financial support from the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant No. 17J02767, and JSPS Overseas Challenge Program for Young Researchers, Grant No. 201880193., Financial support by the Deutsche Forschungsgemeinschaft (DFG)., Funding by the Deutsche Forschungsgemeinschaft (DFG) and the Agence Nationale de la Recherche (ANR) through various programs, This research used resources of the High Performance Computing Center of the Matej Bel University in Banska Bystrica using the HPC infrastructureacquired in Project Nos. ITMS 26230120002 and 26210120002 (Slovak Infrastructure for High Performance Computing) supported by the Research and Development Operational Programme funded by the ERDF, Support by the Research Council of Norway through its Centres of Excellence scheme, Project No. 262695, and through its Mobility Grant scheme, Project No. 261873., Support of the Polish National Science Centre (Grant No. 2016/23/D/ST4/03217)., Support from CONICET by Grant No. PIP 112-20130100361 and FONCYT by Grant No. PICT 2016-2936, Financial support from the Research Council of Norway through its Centres of Excellence scheme(Project No. 262695)., ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Tel Aviv University (TAU), Danmarks Tekniske Universitet = Technical University of Denmark (DTU), Universiteit Leiden, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Norwegian Academy of Science and Letters, Matej Bel University, Technische Universität Braunschweig [Braunschweig], Theoretical Chemistry, AIMMS, Groupe Méthodes et outils de la chimie quantique (LCPQ) [GMO], Physico-Chimie Moléculaire Théorique [PCMT], and Laboratorium für Physikalische Chemie [ETH-LPC]
Subjects: Física Atómica, Molecular y Química, MOLECULAR PROPERTIES, Field (physics), Ciencias Físicas, Implicit solvation, Dirac (software), ELECTRONIC STRUCTURE, General Physics and Astronomy, FOS: Physical sciences, 010402 general chemistry, 01 natural sciences, Polarizable continuum model, QUANTUM CHEMISTRY SOFTWARE, purl.org/becyt/ford/1 [https], Theoretical physics, Physics - Chemical Physics, 0103 physical sciences, Physical and Theoretical Chemistry, Physics::Chemical Physics, Physics, Chemical Physics (physics.chem-ph), ENVIRONMENTAL EFFECTS, 010304 chemical physics, RELATIVISTIC MOLECULAR CALCULATIONS, Multireference configuration interaction, Propagator, purl.org/becyt/ford/1.3 [https], SDG 10 - Reduced Inequalities, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Coupled cluster, Embedding, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], CIENCIAS NATURALES Y EXACTAS
Abstract: DIRAC is a freely distributed general-purpose program system for 1-, 2- and 4-component relativistic molecular calculations at the level of Hartree--Fock, Kohn--Sham (including range-separated theory), multiconfigurational self-consistent-field, multireference configuration interaction, coupled cluster and electron propagator theory. At the self-consistent-field level a highly original scheme, based on quaternion algebra, is implemented for the treatment of both spatial and time reversal symmetry. DIRAC features a very general module for the calculation of molecular properties that to a large extent may be defined by the user and further analyzed through a powerful visualization module. It allows the inclusion of environmental effects through three different classes of increasingly sophisticated embedding approaches: the implicit solvation polarizable continuum model, the explicit polarizable embedding, and frozen density embedding models. DIRAC was one of the earliest codes for relativistic molecular calculations and remains a reference in its field., The following article has been submitted to The Journal of Chemical Physics. After it is published, it will be found at https://aip.scitation.org/toc/jcp/current
Published: 2020

4. Electronic states of (ultra) heavy halogen species with four-component based equation of motion coupled cluster methods

Author: Shee, Avijit, Saue, Trond, Visscher, Lucas, Severo Pereira Gomes, André, Physico-Chimie Moléculaire Théorique ( PCMT ), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 ( PhLAM ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), Department of Chemistry - University of Michigan, University of Michigan [Ann Arbor], Méthodes et outils de la chimie quantique (LCPQ), Laboratoire de Chimie et Physique Quantiques ( LCPQ ), Université Paul Sabatier - Toulouse 3 ( UPS ) -Centre National de la Recherche Scientifique ( CNRS ) -Université Paul Sabatier - Toulouse 3 ( UPS ) -Centre National de la Recherche Scientifique ( CNRS ), Department of Theoretical Chemistry, Vrije Universiteit Amsterdam [Amsterdam] ( VU ), ANR-11-LABX-0005/11-LABX-0005,Cappa,Physiques et Chimie de l’Environnement Atmosphérique ( 2011 ), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, Department of Chemistry, University of Michigan, University of Michigan System-University of Michigan System, Groupe Méthodes et outils de la chimie quantique (LCPQ) (GMO), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Vrije Universiteit Amsterdam [Amsterdam] (VU), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [ PHYS.PHYS.PHYS-CHEM-PH ] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2018

5. Predicting solvent effects on the photoelectron spectra of halide ions with WFT-in-DFT embedding

Author: Bouchafra , Yassine, Shee , Avijit, Réal , Florent, Vallet , Valérie, Severo Pereira Gomes , Andre, Physico-Chimie Moléculaire Théorique ( PCMT ), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 ( PhLAM ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), Department of Chemistry - University of Michigan, University of Michigan [Ann Arbor], ANR-11-LABX-0005/11-LABX-0005,Cappa,Physiques et Chimie de l’Environnement Atmosphérique ( 2011 ), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, University of Michigan, University of Michigan System-University of Michigan System, ANR-11-LABX-0005/11-LABX-0005,Cappa,Physiques et Chimie de l’Environnement Atmosphérique(2011), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), Vallet, Valérie, and Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [ PHYS.PHYS.PHYS-CHEM-PH ] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], ComputingMilieux_MISCELLANEOUS, [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: National audience
Published: 2018

6. Carotenoids: Experimental Ionization Energies and Capacity at Inhibiting Lipid Peroxidation in a Chemical Model of Dietary Oxidative Stress

Author: Alexandre Giuliani, Olivier Dangles, Catherine Caris-Veyrat, Michel Carail, Denis Duflot, Pascale Goupy, Sécurité et Qualité des Produits d'Origine Végétale (SQPOV), Institut National de la Recherche Agronomique (INRA)-Avignon Université (AU), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), U1008, INRA, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Sécurité et Qualité des Produits d'Origine Végétale ( SQPOV ), Institut National de la Recherche Agronomique ( INRA ) -Université d'Avignon et des Pays de Vaucluse ( UAPV ), Synchrotron SOLEIL, Physico-Chimie Moléculaire Théorique ( PCMT ), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 ( PhLAM ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), and Avignon Université (AU)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Subjects: 0301 basic medicine, Antioxidant, Ultraviolet Rays, Linoleic acid, medicine.medical_treatment, Heme, Xanthophylls, Mass spectrometry, medicine.disease_cause, 01 natural sciences, Mass Spectrometry, Lipid peroxidation, Linoleic Acid, 03 medical and health sciences, chemistry.chemical_compound, Materials Chemistry, medicine, Physical and Theoretical Chemistry, Carotenoid, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Ions, Chromatography, 010401 analytical chemistry, food and beverages, beta Carotene, 0104 chemical sciences, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [ PHYS.PHYS.PHYS-CHEM-PH ] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 030104 developmental biology, Atmospheric Pressure, chemistry, Models, Chemical, Xanthophyll, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, Fatty Acids, Unsaturated, Quantum Theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Lipid Peroxidation, Metmyoglobin, Oxidative stress
Abstract: International audience; Carotenoids are important natural pigments and micronutrients contributing to health prevention by several mechanisms, including their electron-donating (antioxidant) activity. In this work, a large series of carotenoids, including 11 carotenes and 14 xanthophylls, have been investigated by wavelength-resolved atmospheric pressure photoionization mass spectrometry (DISCO line of SOLEIL synchrotron), thus allowing the experimental determination of their ionization energy (IE) for the first time. On the other hand, the carotenoids have been also investigated for their ability to inhibit the heme iron-induced peroxidation of linoleic acid in mildly acidic micelles, a simple but relevant chemical model of oxidative stress in the gastric compartment. Thus, the carotenoids can be easily classified from IC50 concentrations deduced from the time dependence of the lipid hydroperoxide concentration. With a selection of two carotenes and three xanthophylls a quantitative analysis is also provided to extract stoichio-kinetic parameters. The influence of the carotenoid structure (number of conjugated carbon−carbon double bonds, presence of terminal six-membered rings, hydroxyl, keto, and/or epoxy groups) on the IE, IC50, and stoichio-kinetic parameters is discussed in details. The data show that the antioxidant activity of carotenes is well correlated to their electron-donating capacity, which itself largely depends on the length of the conjugated polyene chain. By contrast, the IE of xanthophylls is poorly correlated to the polyene chain length because of the strong, and sometimes unexpected, electronic effects of the O-atoms. Although IE remains an approximate predictor of the antioxidant activity of xanthophylls, other factors (interaction with the aqueous phase, competing radical-scavenging mechanisms, the residual activity of the antioxidant’s oxidation products) probably play a significant role.
Published: 2018

7. Theoretical study of the I++ I- mutual neutralization reaction

Author: Badin, Sylvain, Yuan, Xiang, Bourgeois, Pierre-Louis, Gomes, Andre Severo Pereira, Sisourat, Nicolas, Theoretical Chemistry, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Physique - Matière et Rayonnement (LCPMR), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Theoretical Chemistry and Amsterdam Centre for Multiscale Modeling (ACMM) VU University Amsterdam (ACMM), Vrije Universiteit Amsterdam [Amsterdam] (VU), French national supercomputing facilities (Grants No. DARI A0090801859 and No. A0110801859), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Atomic Physics (physics.atom-ph), FOS: Physical sciences, SDG 7 - Affordable and Clean Energy, Physics - Atomic Physics
Abstract: International audience; We have computed the cross sections of the mutual neutralization reaction between I+ and I- for a collision energy varying from 0.001 eV to 50 eV. These cross sections were obtained using the adiabatic potential energy curves of the I2 system computed with a direct relativistic Multi-Reference Configuration Interaction method and a semi-classical approach (i.e. Landau Zener Surface Hopping). We report the cross sections towards the following neutral sates : I(2P3/2)+I(2P3/2), I(2P3/2) + I(2P1/2), I(2P1/2) + I(2P1/2) and I(5p46s) + I(2P3/2). We also discuss the cross sections towards the two following excited ionic states : I- (1S0) + I+ (3P0) and I- (1S0) + I+ (3D2). The results of these calculations are in accordance with recent experimental measurements conducted in the double ion ring DESIREE in Stockholm. These results can be used to model iodine plasma kinetics and thus to improve our understanding of the latter.
Published: 2023

8. Coordination and thermodynamic properties of aqueous protactinium(<scp>v</scp>) by first-principle calculations

Author: Hanna Oher, Jérémy Delafoulhouze, Eric Renault, Valérie Vallet, Rémi Maurice, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), This work was supported by the Région des Pays de la Loire (RCT-PaPAn project) and by the French National Research Agency (ANR-21-CE29-0027, LABEX CaPPA/ANR-11-LABX-0005-01 and I-SITE ULNE/ANR-16-IDEX-0004 ULNE). HPC resources from CCIPL (Centre de Calcul Intensif des Pays de la Loire) were used., ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: Chemical Physics (physics.chem-ph), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Physics - Chemical Physics, FOS: Physical sciences, General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract: International audience; Protactinium (Z = 91) is a very rare actinide with peculiar physico-chemical properties. Indeed, although one may naively think that it behaves similarly to either thorium or uranium by its position in the periodic table, it may in fact follow its own rules. Because of the quite small energy gap between its valence shells (in particular the 5f and 6d ones) and also the strong influence of relativistic effects on its properties, it is actually a challenging element for theoretical chemists. In this article, we combine experimental information, chemical arguments and standard first-principle calculations, complemented by implicit and explicit solvation, to revisit the stepwise complexation of aqueous protactinium(V) with sulfate and oxalate dianionic ligands (SO42- and C2O42-, respectively). From a methodological viewpoint, we notably conclude that it is necessary to at least saturate the coordination sphere of protactinium(V) to reach converged equilibrium constant values. Furthermore, in the case of single complexations (i.e. with one sulfate or oxalate ligand bound in the bidentate fashion), we show that it is necessary to maintain the coordination of one hydroxyl group, thought of in the [PaO(OH)]^3+ precursor, to obtain coherent complexation constants. Therefore, we predict that this hydroxyl group is maintained in the formation of 1:1 complexes while we confirm that it is withdrawn when coordinating three sulfate or oxalate ligands. Finally, we stress that this work is a first step toward the future use of theoretical predictions to elucidate the enigmatic chemistry of protactinium in solution.
Published: 2023

9. Exploring the complexation of curium(III) and europium(III) with aqueous phosphates: a combined experimental and ab initio study

Author: Réal, Florent, Huittinen, Nina, Jessat, Isabelle, Vallet, Valérie, Jordan, Norbert, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

10. Complexation of neptunium(V) with aqueous phosphate using a dual experimental and quantum chemical approach

Author: Miladi, Eya, Réal, Florent, Vallet, Valérie, Jordan, Norbert, Huittinen, Nina, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

11. Coordination and thermodynamic properties of aqueous protactinium(V) by computational chemistry techniques

Author: Oher, Hanna, Delafoulhouze, Jeremy, Renault, Eric, Vallet, Valérie, Maurice, Rémi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

12. The electronic structure of actinides tailored by relativistic quantum chemistry approaches: applications to X-ray spectroscopies

Author: Misael, Wilken, Vallet, Valérie, Severo Pereira Gomes, André, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

13. Complexation of Cm(III) and Eu(III) with aqueous phosphate: a combined luminescence, thermodynamic, and ab initio study

Author: Jordan, Norbert, Jessat, Isabelle, Huittinen, Nina, Réal, Florent, Vallet, Valérie, Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

14. A theoretical study of chemistry and speciation of protactinium

Author: Oher, Hanna, Vallet, Valérie, Maurice, Rémi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

15. Effect of inorganic ligands on Pa5+ and PaO3+ relative stabilities: A computational study

Author: Shaaban, Tamara, Vallet, Valérie, Réal, Florent, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

16. Exploring luminescence properties of uranyl-based complexes by TRLFS and ab initio method

Author: Vallet, Valérie, Oher, Hanna, Réal, Florent, Severo Pereira Gomes, André, Wilson, Richard, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemical Sciences and Engineering Division [Argonne], Argonne National Laboratory [Lemont] (ANL), ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience
Published: 2023

17. The performance of approximate equation of motion coupled cluster for valence and core states of heavy element systems

Author: Halbert, Loïc, Gomes, Andre Severo Pereira, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), French Ministry of Higher Education and Research, region Hauts de France council and European Regional Development Fund (ERDF), Project CPER WAVETECH, French national supercomputing facilities (grants DARI A0090801859, A0110801859), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019)
Subjects: Chemical Physics (physics.chem-ph), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Physics - Chemical Physics, FOS: Physical sciences
Abstract: The equation of motion coupled cluster singles and doubles model (EOM-CCSD) is an accurate, black-box correlated electronic structure approach to investigate electronically excited states and electron attachment or detachment processes. It has also served as a basis for developing less computationally expensive approximate models such as partitioned EOM-CCSD (P-EOM-CCSD), the second-order many-body perturbation theory EOM (EOM-MBPT(2)), and their combination (P-EOM-MBPT(2)) [S. Gwaltney et al., Chem. Phys. Lett. 248, 189-198 (1996)]. In this work we outline an implementation of these approximations for four-component based Hamiltonians and investigate their accuracy relative to EOM-CCSD for valence excitations, valence and core ionizations and electron attachment, and this for a number of systems of atmospheric or astrophysical interest containing elements across the periodic table. We have found that across the different systems and electronic states of different nature considered, partition EOM-CCSD yields results with the largest deviations from the reference, whereas second-order based approaches tend show a generally better agreement with EOM-CCSD. We trace this behavior to the imbalance brought about by the removal of excited state relaxation in the partition approaches, with respect to degree of electron correlation recovered., Comment: 5 figures, 4 tables
Published: 2023

18. Protein - ligand interactions from a quantum fragmentation perspective : the case of the SARS-CoV-2 main protease interacting with α−ketoamide inhibitors

Author: Genovese, Luigi, Dawson, William, Nakajima, Takahito, Cristiglio, Viviana, Vallet, Valérie, Masella, Michel, Laboratory of Atomistic Simulation (LSIM), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), RIKEN Center for Computational Science [Kobe] (RIKEN CCS), RIKEN - Institute of Physical and Chemical Research [Japon] (RIKEN), Institut Laue-Langevin (ILL), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Biologie Structurale et Radiobiologie (LBSR), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), TGCC HPC resources under the allocation 2019-2020[A0070307078] and the Grand Challenge allocation [GC0429] made by GENCI, MAX EU Center of Excellence, CPER CLIMIBIO (European Regional Development Fund, Hauts de France council, French Ministry of Higher Education and Research), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; We present a hybrid, multi-method, computational scheme for protein/ligand systems well suited to be used on modern and forthcoming massively parallel computing systems. The scheme relies on a multi-scale polarizable Molecular Modeling, MM, approach to perform MD simulations and on an efficient DFT Linear Scaling method to post-process simulation snapshots. We use this scheme to investigate recent α-ketoamide inhibitors targeting the main protease of the SARS-CoV-2 virus. We assessed the reliability and the coherence of the hybrid scheme in particular by checking the ability of MM and DFT to reproduce results from high-end ab initio computations regarding such inhibitors. The DFT approach enables an a posterior fragmentation of the system and an investigation into the strength of interaction among identified fragment pairs.
Published: 2023

19. How does bending the uranyl unit influence its spectroscopy and luminescence

Author: Hanna Oher, André Severo Pereira Gomes, Richard E. Wilson, David D. Schnaars, Valérie Vallet, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Chemical Sciences and Engineering Division [Argonne], Argonne National Laboratory [Lemont] (ANL), Deutsche Forschung Gemeinschaft JA 2329/6, I-SITE ULNE projects OVERSEE, I-SITE ULNE MESONM International Associated Laboratory (LAI), French Ministry of Higher Education and Research, Région Hauts de France council and European Regional Development Fund (ERDF) project CPER CLIMIBIO, WaveTech, French national supercomputing facilities (grants DARI A0130801859, A0110801859, U.S. DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences Geological and Biosciences Division,Heavy Element Chemistry program under Contract DE-AC02-06CH11357, ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry
Abstract: International audience; Bent uranyl complexes can be formed with chloride ligands and 1,10-phenanthroline (phen) ligands bound to the equatorial and axial planes of the uranyl(VI) moiety, as revealed by the crystal structures, IR and Raman spectroscopy and quantum chemical calculations. With the goal of probing the influence of chloride and phenanthroline coordination enforcing the bending on the absorption and emission spectra of this complex, spin-orbit time-dependent density functional theory calculations for the bare uranyl complexes as well as for the free UO2Cl2 subunit and the UO2Cl2(phen)2 ligand were performed. The emission spectra has been fully simulated by ab initio methods and compared to experimental photoluminescence spectra, recorded for the first time for UO2Cl2(phen)2. Notably, the bending of uranyl in UO2Cl2 and UO2Cl2(phen)2 triggers excitations of the uranyl bending mode, yielding a denser luminescence spectrum.
Published: 2023

20. Structural, dynamical, and transport properties of the hydrated halides: How do At- bulk properties compare with those of the other halides, from F- to I-?

Author: Michel Masella, Tahra Ayed, Yansel Omar Guerrero Martínez, André Severo Pereira Gomes, Valérie Vallet, Florent Réal, Nicolas Galland, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Biologie et de Technologies de Saclay (IBITECS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-10-BLAN-0807,EXCAT3,EXploration de la Chimie de At(III) en solution. Vers de nouvelles voies de marquage pour la médecine nucléaire?(2010), European Project: 323300,EC:FP7:Fission,FP7-Fission-2012,TALISMAN(2013), Physico-Chimie Moléculaire Théorique ( PCMT ), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 ( PhLAM ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation ( CEISAM ), Université de Nantes ( UN ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Biologie et de Technologies de Saclay ( IBITECS ), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives ( CEA ), ANR-11-LABX-0005/11-LABX-0005,Cappa,Physiques et Chimie de l’Environnement Atmosphérique ( 2011 ), ANR-10-BLAN-0807,EXCAT3,EXploration de la Chimie de At(III) en solution. Vers de nouvelles voies de marquage pour la médecine nucléaire? ( 2010 ), European Project : 323300,EC:FP7:Fission,FP7-Fission-2012,TALISMAN ( 2013 ), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010304 chemical physics, Electronic correlation, Hydrogen bond, Chemistry, Ab initio, Solvation, General Physics and Astronomy, Halide, Thermodynamics, 010402 general chemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Ion, Molecular dynamics, [ PHYS.PHYS.PHYS-CHEM-PH ] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 13. Climate action, Polarizability, Computational chemistry, TheoryofComputation_ANALYSISOFALGORITHMSANDPROBLEMCOMPLEXITY, 0103 physical sciences, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; The properties of halides from the lightest, Fuoride (F-), to the heaviest, astatide (At-), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force- eld parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I- and At-, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I- and At- in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F-, Cl-, and Br- ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At- in liquid water at ambient conditions to be 68 kcal mol-1, a value also close the I- one, about 70 kcal mol-1. In all, our simulation results for I- are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At- ion are predictive, as no theoretical or experimental data are available to date.
Published: 2016

21. Modeling environment effect on heavy-element compounds

Author: Olejniczak, Małgorzata, Vallet, Valérie, Severo Pereira Gomes, André, Centre of New Technologies, Medical University of Warsaw - Poland, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), he French Ministry of Higher Education and Research, region Hauts de France council and European Regional Development Fund (ERDF) projects CPER CLIMIBIO and WAVETECH, Deutsche Forschungsgemeinschaft JA 2329/6-1, Polish National Science Centre (NCN) (grantnumber 2020/38/E/ST4/00614, ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021), and ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: Modeling the behavior of molecular complexes containing one or more heavy elements by means of electronic structure calculations, in particular when attempting to understand their molecular properties, is a very challenging task since one has to account not only for electron correlation and relativistic effects but in many cases consider the effect of other species in their vicinity as well. In this chapter, we address how such environment effects can be taken into account in a computationally efficient manner through different flavors of so-called embedding theories, underscoring the applicability, strengths, and weaknesses of the most commonly used approaches.
Published: 2023

22. Modeling polonium complexes in solution

Author: Zhutova, Nadiya, Réal, Florent, Renault, Eric, Vallet, Valérie, Maurice, Rémi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Abstract: International audience; Polonium is a heavy and rare element standing under the number 84 on the Periodic Table. It is a naturally occurring element, though its abundance is among the weakest ones. It is highly toxic, which hinders experimental studies aiming at revealing its properties. Nevertheless, polonium was used as a heat source in the space industry, as an alpha-emission source, or as a static eliminator, before cheaper and safer alternatives replaced it. It is also a famous poison, with currently no good enough antidote. A better understanding of its chemistry could potentially help in better detecting it and also characterizing its speciation in natural media and industry and also in designing better cure in the case of ingestion. However, the available quantities and the complex manipulation of this element make its characterization arduous. In this context, we perform quantum chemistry calculations to predict the properties of polonium species. In our project, we study polonium complexes in the gas phase and in solution. We consider its most stable oxidation state in solution, i.e. +IV. Following previous work [1,2], two families of complexes were first chosen for performing a methodological study in the gas phase. While the [Po(H2O)n]4+ (n = 1–9) series was selected to get fundamental knowledge of hydration, the chlorinated [PoClm]4–m (m = 1–8) complexes were studied because of experimental evidence for the formation of such species in solution. As an extension to a benchmark study in the gas phase on geometries and interaction energies, ground state bonding descriptors were obtained [3]. Therefore, information on coordination numbers and chemical bonding were both derived. Following the idea to connect with established experimental data, state-of-the-art excited-state calculations have been performed on two potentially occurring chlorinated complexes, revealing once more the difficulty of interpreting from scratch the few spectra that are available for polonium species. We thus emphasize the need for performing more calculations of predictive quality to unravel this enigmatic chemistry. References:[1] R. Ayala, J. M. Martinez, R. R. Pappalardo, A. Muñoz-Paez and E. Marcos Sánchez, J. Phys. Chem. B, 2008, 112, 5416–5422.[2] A. Stoanov, J. Champion and R. Maurice, Inorg. Chem., 2019, 58, 7036-7043.[3] N. Zhutova, F. Réal, V. Vallet and R. Maurice, Phys. Chem. Chem. Phys., 2022, 24, 26180-26189.
Published: 2023

23. Core excitations and ionizations of uranyl in Cs2UO2Cl4 from relativistic embedded damped response time-dependent density functional theory and equation of motion coupled cluster calculations

Author: Misael, W.A. (Wilken Aldair), Severo Pereira Gomes, A. (Andre), and Physico-Chimie Moléculaire Théorique [PCMT]
Abstract: X-ray spectroscopies, by their high selectivity and sensitivity to the chemical environment around the atoms probed, provide significant insight into the electronic structure of molecules and materials. Interpreting experimental results requires reliable theoretical models, accounting for environment, relativistic, electron correlation, and orbital relaxation effects in a balanced manner. = In this work, following up on prior work for valence processes [A. S. P. Gomes et al., Phys. Chem. Chem. Phys. 15, 15153 (2013)], we present a protocol for the simulation of core excited spectra (with damped response time-dependent density functional theory, 4c-DR-TD-DFT) and ionization energies (with the core-valence separated equation of motion coupled cluster theory, 4c-CVS-EOM-IP) based on the Dirac-Coulomb Hamiltonian, while environment effects are accounted for through the frozen density embedding (FDE) method. We showcase this approach for the uranium M4-, L3-edge and oxygen K-edge of uranyl tetrachloride UO2Cl42- in a host Cs2UO2Cl4 crystal. We have found that the 4c-DR-TD-DFT simulations yield excitation spectra that very closely match the experiment for the uranium M4 and oxygen K-edges, with good agreement for the broad experimental spectra for the L3-edge. By investigating the sensitivity of spectral shapes to the lifetimes, and by decomposing each peak into its components, we have been able to correlate our results with angle-resolved spectra. We have observed that for the uranium M4 edge, a simplified model for uranyl tetrachloride-in which an embedding potential replaces the chloride equatorial ligands-closely matches the spectral profile obtained for the uranyl tetrachloride system.
Published: 2023

24. Etude théorique de la réaction de neutralisation I+ - I

Author: Badin, Sylvain, Yuan, Xiang, Bourgeois, Pierre-Louis, Gomes, Andre Severo Pereira, Sisourat, Nicolas, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), and Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics]
Abstract: We have computed the cross sections of the mutual neutralization reaction between I + and I − for a collision energy varying from 0.001 eV to 50 eV. These cross sections were obtained using the adiabatic potential energy curves of the I2 system computed with a direct relativistic Multi-Reference Configuration Interaction method and a semi-classical approach (i.e. Landau Zener Surface Hopping). We report the cross sections towards the following neutral sates : I(2 P 3/2)+I(2 P 3/2), I(2 P 3/2) + I(2 P 1/2), I(2 P 1/2) + I(2 P 1/2) and I(5p 4 6s) + I(2 P 3/2). We also discuss the cross sections towards the two following excited ionic states : I − (1 S0) + I + (3 P0) and I − (1 S0) + I + (3 D2). The results of these calculations are in qualitative accordance with recent experimental measurements conducted in the double ion ring DESIREE in Stockholm. These results can be used to model iodine plasma kinetics and thus to improve our understanding of the latter.
Published: 2023

25. Uranium(<scp>iv</scp>) alkyl cations: synthesis, structures, comparison with thorium(<scp>iv</scp>) analogues, and the influence of arene-coordination on thermal stability and ethylene polymerization activity

Author: Nicholas R. Andreychuk, Balamurugan Vidjayacoumar, Jeffrey S. Price, Sophie Kervazo, Craig A. Peeples, David J. H. Emslie, Valérie Vallet, André S. P. Gomes, Florent Réal, Georg Schreckenbach, Paul W. Ayers, Ignacio Vargas-Baca, Hilary A. Jenkins, James F. Britten, Department of Chemistry, McMaster University, McMaster University [Hamilton, Ontario], Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), University of Manitoba [Winnipeg], NSERC of Canada for a Discovery Grant, Digital Research Alliance of Canada (previously Compute Canada) for a 2020 Resources for Research Groups (RRG) grant, NSERC, Digital Research Alliance of Canada, Canada Research Chairs for funding and computational resources, Government of Ontario for an Ontario Graduate Scholarship (OGS), McMaster University for a Richard Fuller Memorial Scholarship, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry
Abstract: International audience; Reaction of [(XA2)U(CH2SiMe3)2] (1; XA2 = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9- dimethylxanthene) with 1 equivalent of [Ph3C][B(C6F5)4] in arene solvents afforded the arene-coordinated uranium alkyl cations, [(XA2)U(CH2SiMe3)(hn-arene)][B(C6F5)4] {arene = benzene (2), toluene (3), bromobenzene (4) and fluorobenzene (5)}. Compounds 2, 3, and 5 were crystallographically characterized, and in all cases the arene is π-coordinated. Solution NMR studies of 2-5 suggest that the binding preferences of the [(XA2)U(CH2SiMe3)]+ cation follow the order: toluene ≈ benzene > bromobenzene > fluorobenzene. Compounds 2-4 generated in C6H5R (R = H, Me or Br, respectively) showed no polymerization activity under 1 atm of ethylene. By contrast, 5 and 5-Th (the thorium analogue of 5) in fluorobenzene at 20 and 70 °C achieved ethylene polymerization activities between 16 800 and 139 200 g mol-1 h-1 atm-1, highlighting the extent to which common arene solvents such as toluene can suppress ethylene polymerization activity in sterically open f-element complexes. However, activation of [(XA2) An(CH2SiMe3)2] {M = U (1) or Th (1-Th)} with [Ph3C][B(C6F5)4] in n-alkane solvents did not afford an active polymerization catalyst due to catalyst decomposition, illustrating the critical role of PhX (X = H, Me, Br or F) coordination for alkyl cation stabilization. Gas phase DFT calculations, including fragment interaction calculations with energy decomposition and ETS-NOCV analysis, were carried out on the cationic portion of 2'-Th, 2', 3' and 5' (analogues of 2-Th, 2, 3 and 5 with hydrogen atoms in place of ligand backbone methyl and tert-butyl groups), providing insight into the nature of actinide–arene bonding, which decreases in strength in the order 2'-Th > 2' ≈ 3' > 5'.
Published: 2022

26. Photodynamics of lanthanide and actinide complexes

Author: Vallet, Valérie, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience
Published: 2022

27. CRYSTAL23: A Program for Computational Solid State Physics and Chemistry

Author: Alessandro Erba, Jacques K. Desmarais, Silvia Casassa, Bartolomeo Civalleri, Lorenzo Donà, Ian J. Bush, Barry Searle, Lorenzo Maschio, Loredana Edith-Daga, Alessandro Cossard, Chiara Ribaldone, Eleonora Ascrizzi, Naiara L. Marana, Jean-Pierre Flament, Bernard Kirtman, Dipartimento di Chimica, Università degli studi di Torino = University of Turin (UNITO), STFC Rutherford Appleton Laboratory (RAL), Science and Technology Facilities Council (STFC), Dipartimento di Chimica IFM and NIS, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Biochemistry [Santa Barbara], University of California [Santa Barbara] (UC Santa Barbara), and University of California (UC)-University of California (UC)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Computer Science Applications
Abstract: International audience; The Crystal program for quantum-mechanical simulations of materials has been bridging the realm of molecular quantum chemistry to the realm of solid state physics for many years, since its first public version released back in 1988. This peculiarity stems from the use of atom-centered basis functions within a linear combination of atomic orbitals (LCAO) approach and from the corresponding efficiency in the evaluation of the exact Fock exchange series. In particular, this has led to the implementation of a rich variety of hybrid density functional approximations since 1998. Nowadays, it is acknowledged by a broad community of solid state chemists and physicists that the inclusion of a fraction of Fock exchange in the exchange-correlation potential of the density functional theory is key to a better description of many properties of materials (electronic, magnetic, mechanical, spintronic, lattice-dynamical, etc.). Here, the main developments made to the program in the last five years (i.e., since the previous release, Crystal17) are presented and some of their most noteworthy applications reviewed.
Published: 2022

28. Probing luminescence properties and photo reactivity of f-element complexes with ab initio methods

Author: Vallet, Valérie, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience
Published: 2022

29. Environmental Effects with Frozen-Density Embedding in the Real-Time Time-Dependent Dirac-Kohn-Sham framework

Author: de Santis, Matteo, Vallet, Valérie, Severo Pereira Gomes, André, Belpassi, Leonardo, Storchi, Loriano, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Istituto di Scienze e Tecnologie Chimiche 'Giulio Natta' (SCITEC), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Dipartimento di Farmacia, Universita G. d Annunzio, Via dei Vestini, 66100 Chieti, Italy, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID, and Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique - - CompRIXS2019 - ANR-19-CE29-0019 - AAPG2019 - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Frozen Density Embedding (FDE)[1,2] represents a versatile embedding scheme which allows to model complex molecular systems by partitioning the total system into sub-units: the environmental effects onto a given subsystem is described by accounting quantum mechanically for the surrounding subsystems through their electron density.The accurate modeling of properties of matter when heavy elements are involved requires the inclusion of relativistic corrections. The Dirac-Kohn-Sham (DKS) method allows one to treat electron correlation and relativistic effects on the same footing.The response of electrons in atoms and molecules to an applied external electro-magnetic field can be efficiently treated employing Time-Dependent Density Functional Theory (TDDFT) in the real-time domain (RT-TDDFT)[3].We extend the full 4-component relativistic RT-TDDKS[4] method, as implemented in the BERTHA code, to include environmental and confinement effects with the FDE scheme (RT-TDDKS-in-DFT FDE)[5].Moreover, we demonstrate that the implementation of rather complex numerical algorithms can be enormously facilitated by BERTHA’s python API (PyBERTHA) which, besides all the well-known Python advantages, eases the interoperability with other FDE implementations available through the PyADF framework.References:1. Wesolowski, T. A.; Warshel, A. Frozen density functional approach for ab initio calculations of solvated molecules. J. Chem. Phys. 1993, 97, 8050–8053. 2. Höfener, S.; Gomes, A. S. P.; Visscher, L. Molecular properties via a subsystem density functional theory formulation: a common framework for electronic embedding. J. Chem Phys, 2012, 136(4), 044104.3. Lopata, K.; Govind, N. Modeling Fast Electron Dynamics with Real-Time Time-Dependent Density Functional Theory: Application to Small Molecules and Chromophores. J. Chem. Theory Comput. 2011, 7, 1344–13554. De Santis, M.; Storchi, L.; Belpassi, L.; Quiney, H. M.; Tarantelli, F. PyBERTHART: A Relativistic Real-Time Four-Component TDDFT Implementation Using Prototyping Techniques Based on Python. J. Chem. Theory Comput. 2020, 16, 2410–2429. 5. De Santis, M.; Sorbelli, D.; Vallet, V.; Gomes, A. S. P.; Storchi, L.; Belpassi, L. Frozen-Density Embedding for including environmental effects in the Dirac-Kohn-Sham theory: an implementation based on density fitting and prototyping techniques. https://doi.org/10.48550/arXiv.2205.05523
Published: 2022

30. Assessing MP2 frozen natural orbitals for relativistic electronic structure

Author: Yuan, Xiang, Visscher, Lucas, Severo Pereira Gomes, André, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam [Amsterdam] (VU), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID, and Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique - - CompRIXS2019 - ANR-19-CE29-0019 - AAPG2019 - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: National audience; The O(N6) computation cost is a bottleneck preventing performing Coupled-Cluster (CC) on large systems, particularly when employing 4- component based relativistic Hamiltonians, for which in practice one often uses uncontracted basis set generating large virtual molecular orbitalspaces.The canonical Hartree-Fock (HF) orbitals are not the most compact representation for post HF method. On other hand, using natural orbital is an efficient way to reduce the orbital space and maintains most of the accuracy. We therefore implemented the MP2 frozen natural orbital (FNO) method [1] in the Exacorr code [2], with the particularity that our implementation can generate both complex and quaternion FNOs, and also express these in AO basis. It also allows us to obtain CCSD natural orbitals on AO basis, which can be subsequently used in analysis. We have investigated the orbital truncation errors in both correlation energy and molecular properties including dipole, quadrupole moment, electric filed gradient, for hydrogen halides HX (X=F, Cl, Br, I, At, Ts), and parity violation for the H2X2 (X= O, S, Se, Te, Po) molecules. We find that FNO indeed accelerates rapidly the correlation energy convergence. For properties, truncated FNO spaces seem to slightly outperform canonical HF orbitals, and to provide reliable estimates for the molecular properties obtained for complete virtual spaces [3].Reference[1] T. L. Barr, E. R. Davidson, Phys. Rev. A 1970, 1, 644; A. G. Taube, R. J. Bartlett, J. Chem. Phys. 2008, 128, 164101[2] J. V. Pototschnig, A. Papadopoulos, D. I. Lyakh, M. Repisky, L. Halbert, A. S. P. Gomes, H- JAa. Jensen, L. Visscher, J. Chem. Theory. Comput. 2021, 17, 5509[3] X. Yuan, L. Visscher, ASP. Gomes, J. Chem. Phys. 2022, arXiv:2202.01146
Published: 2022

31. Exploring luminescence properties of uranyl-based complexes by TRLFS and ab initio method

Author: Vallet, Valérie, Oher, Hanna, Réal, Florent, Vercouter, Thomas, Severo Pereira Gomes, André, Wilson, Richard, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Chemical Sciences and Engineering Division [Argonne], Argonne National Laboratory [Lemont] (ANL), ANR-16-IDEX-0004,ULNE,ULNE(2016), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), Vallet, Valérie, ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID, and Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Uranyl complexes have been the subject of many research works for fundamental chemistry of actinides, environmental issues, or nuclear fuel cycle processes. The formation of various uranyl complexes, with organic and inorganic ligands in solution must be characterized for a better understanding of U(VI) speciation. As uranyl-ligand interactions and the symmetry of the complexes affect the electronic structure of U(VI) and thus its luminescence properties, time-resolved laser induced fluorescence spectroscopy (TRLFS) is one of the major techniques to characterize U(VI) complexes, with high sensitivity and selectivity. However, most of the relevant systems have complex chemical composition in solution and the identification of each species from spectroscopic data is challenging.In our study, the synergy between TRLFS and ab initio-based interpretation appears as a promising route for complexation data. Luminescence spectra of uranyl complexes in solution show in general a narrow energetical range about 6000 cm-1 and we can identify a single electronic transition between the initial and target states with the vibrationally resolved band [1]. The main challenge consists in exploiting a computationally cheap and effective theoretical approach, in a relativistic context, to characterize the main spectral parameters of the ground and luminescent states of symmetrical uranyl compounds (i.e. UO2Cl42-, UO2F53-, UO2(CO3)34-, UO2(NO3)L2) with different organic or inorganic counter ions after the photo-excitation. We will illustrate that TD-DFT with the CAM-B3LYP functional is able to provide accurate excitation/emission energies for these systems, together with accurate vibronic progressions allowing the assignment of experimental data.As a benchmark system serving the purpose of assessing the accuracy of our theoretical protocol, the uranyl tetrachloride UO2Cl42- was selected because of the extensive amount of structural and spectroscopic data available [2]. A good agreement was found between ours and previously obtained theoretical data (structural parameters, orbitals nature, excitation energies) [3]; the final luminescence spectrum is in remarkable agreement with our TRLFS measurements [4]. We will also quantify the effects of organic or inorganic counterions [5, 6], along with that of first-sphere ligands that might perturb the uranyl(VI) moiety.This work showcases how one can predict vibrationally resolved spectra to assign the recorded TRLFS data, and shed light on the relationship between the uranyl coordination and its luminescence properties.[1] J. Visnak et al. (2006) EPJ Web Conf. 128, 02002.[2] R.G. Denning et al. (1991) Chem. Phys. Lett. 180, 101.[3] K. Pierloot et al. (2005) J. Chem. Phys. 123, 204309.[4] H. Oher et al. (2020) Inorg. Chem. 59, 5896.[5] H. Oher et al. (2020) Inorg. Chem. 59, 15036.[6] H. Oher et al. (2022) Inorg. Chem. 61, 890.
Published: 2022

32. Relativistic correlated electronic structure and the calculation of accurate ground-state, core and valence properties of heavy element species

Author: Halbert, Loïc, Yuan, Xiang, Réal, Florent, Vallet, Valérie, Severo Pereira Gomes, André, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), DE-AC05-00OR22725, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), ANR-16-IDEX-0004,ULNE,ULNE(2016), Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique - - CompRIXS2019 - ANR-19-CE29-0019 - AAPG2019 - VALID, and ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Accurate electronic structure calculations have become an indispensable tool to understand the molecular properties of heavy and superheavy elements. Such approaches help make sense of the underlying complex physical processes probed by experiments, or in the case such experiments are unfeasible due to the heavy elements’ radiotoxicity.In this presentation I will outline our contributions to developments of coupled cluster approaches based on four-component Hamiltonians for ground-state properties as well as for valence and core excitation and ionization spectra [1-4], and their application to investigating heavy and super heavy elements [2, 3, 5].Furthermore, I will outline how these can be combined with more approximate approaches through embedding theories [6], to enable the investigation of heavy element species in complex environments such as in solution.Funding: ANR-11-LABX-0005-01, ANR-19-CE29-0019, ANR-16-IDEX-0004, DE-AC05- 00OR22725.References[1] J. Pototschnig et al., J. Chem. Theory Comput. (2021) 17, 5509 10.1021/acs.jctc.1c00260 [2] X. Yuan, L. Visscher, A. S. P. Gomes, J. Chem. Phys. (in press) (2022). 10.1063/5.0087243[3] A. Shee, T. Saue, L. Visscher, A. S. P. Gomes, J. Chem. Phys. (2018) 149, 174113 10.1063/1.5053846[4] L. Halbert, M. L. Vidal, A. Shee, S. Coriani, A. S. P. Gomes, J. Chem. Theory Comput. (2021) 17, 3583 10.1021/acs.jctc.0c01203[5] S. Kervazo, F. Réal, F. Virot, A. S. P. Gomes, V. Vallet, Inorg. Chem. (2019) 58, 14507 10.1021/acs.inorgchem.9b02096[6] Y. Bouchafra, A. Shee, F. Réal, V. Vallet, A. S. P. Gomes, Phys. Rev. Lett. (2018) 121, 266001 10.1103/PhysRevLett.121.266001
Published: 2022

33. X-ray Absorption Spectra and Photoionization of Actinide Compounds with Relativistic Electronic Structure Approaches

Author: Misael, Wilken, Severo Pereira Gomes, André, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Vallet, Valérie, Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique - - CompRIXS2019 - ANR-19-CE29-0019 - AAPG2019 - VALID, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, and ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: National audience
Published: 2022

34. Geometries, interaction energies and bonding in [Po(H2O)n]4+ and [PoCln]4-n complexes

Author: Nadiya Zhutova, Florent Réal, Valérie Vallet, Rémi Maurice, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), MITI of CNRS (80|Prime project MSM4Po), HPC resources from the CCIPL (‘‘Centre de calcul intensif des Pays de la Loire’’), French Ministry of Higher Education and Research, region Hauts de France council and European Regional Development Fund (ERDF) project CPER CLIMIBIO., ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: Chemical Physics (physics.chem-ph), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Physics - Chemical Physics, General Physics and Astronomy, FOS: Physical sciences, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; Polonium (Z = 84) is one of the rarest elements on Earth. More than a century after its discovery, its chemistry remains poorly known and even basic questions have not yet been satisfactorily addressed. In this work, we perform a systematic study of the geometries, interactions energies and bonding in basic polonium(IV) species, namely the hydrated [Po(H2O)n]4+ and chlorinated [PoCl2]4-n complexes by means of gas-phase electronic structure calculations. We show that while up to nine water molecules can fit in the first coordination sphere of the polonium(IV) ion, its coordination sphere can already be filled with eight chloride ligands. Capitalising on previous theoretical studies, a focused methodological study based on interaction energies and bond distances allows us to validate the MP2/def2-TZVP level of theory for future ground-state studies. After discussing the similarities and differences between complexes with the same number of ligands, we perform topological analyses of the MP2 electron densities in the quantum theory of atoms in molecules (QTAIM) fashion. While the water complexes display typical signatures of closed-shell interactions, we reveal large Po–Cl delocalisation indices, especially in the hypothetical [PoCl]3+ complex. This “enhanced” covalency opens the way for a significant spin–orbit coupling (SOC) effect on the corresponding bond distance, which has been studied using two independent approaches (i.e. one a priori and one a posteriori). We finally conclude by stressing that while the SOC may not affect much the geometries of high-coordinated polonium(IV) complexes, it should definitely not be neglected in the case of low-coordinated ones.
Published: 2022

35. Complexation of Cm(III) with aqueous phosphates at elevated temperatures: a luminescence, thermodynamic, and ab initio study

Author: Jordan, Norbert, Huittinen, Nina, Jessat, Isabelle, Réal, Florent, Vallet, Valérie, Starke, Sebastian, Eibl, Manuel, Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Information Services and Computing, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, and ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; The incorporation of actinides in lanthanide phosphate matrices crystallizing in the monazite structure has been intensely investigated in the past decades due to the relevance of these monazites as potential ceramic host phases for the immobilization of specific high level radioactive waste (HLW) streams [1-3]. In recent years, understanding the incorporation behaviour of trivalent dopants in the LnPO4•xH2O rhabdophane structure has been given more attention [4,5]. Rhabdophane is the hydrated phosphate precursor in the synthesis of monazites through precipitation routes and a potential secondary mineral controlling actinide solubility in dissolution and re-precipitation reactions of monazite host-phases. Despite the large interest in lanthanide phosphates and the interaction of actinides with these solids, very little data [6-8] is available on the complexation of lanthanides and actinides with aqueous phosphates, even though these complexation reactions precede any aqueous synthesis of monazite ceramics and are expected to occur in natural waters as well as in the proximity of monazite-containing HLW repositories. In many cases, an independent spectroscopic validation of the stoichiometry of the proposed complexes, is also missing. Both from the perspective of aqueous rhabdophane synthesis, which is often carried out at elevated temperatures, and heat-generating HLW immobilization in monazites, the lanthanide and actinide complexation reactions with aqueous phosphates under ambient conditions should be complemented with data obtained at higher temperatures.In the present work, laser-induced luminescence spectroscopy was used to study the complexation of Cm(III) (1.15×10-8 to 1.15×10-7 M) as a function of total phosphate concentration (0 to 0.08 M) in the temperature regime 25-90 °C, using NaClO4 as a background electrolyte (I = 0.5 to 3.0 M). These studies have been conducted in the acidic pH-range (−log10 [H+] = 1.00, 2.52, 3.44, and 3.65) to avoid precipitation of solid Cm rhabdophane. For the first time, in addition to the presence of CmH2PO42+ already evidenced before [6,7], the formation of Cm(H2PO4)2+ was unambiguously established from the luminescence spectroscopic data collected at the various H+ concentrations previously mentioned [8].The conditional complexation constants of both aqueous complexes were found to increase upon rising ionic strength and temperature. Extrapolation of the obtained complexation constants to infinite dilution at 25 °C was performed by applying the Specific Ion Interaction Theory (SIT) [9]. The obtained log10 β° values for CmH2PO42+ and Cm(H2PO4)2+ were 0.45 ± 0.04 and 0.08 ± 0.07 [8], respectively, for reactions 1 and 2 below:Cm3+ + H3PO4 ⇌ CmH2PO42+ + H+ (1)Cm3+ + 2 H3PO4 ⇌ Cm(H2PO4)2+ + 2 H+ (2)The ion interaction coefficients ε(CmH2PO42+;ClO4-) = 0.17 ± 0.04 and ε(Cm(H2PO4)2+;ClO4-) = −0.10 ± 0.06 were derived at 25 °C [8]. Temperature-dependent conditional complexation constants for the identified species were obtained from the recorded luminescence emission spectra. They were subsequently extrapolated to I =0 M, assuming that the ion interaction parameters obtained at 25 °C are not significantly impacted by the temperature increase from 25 °C to 90 °C [6]. Using the integrated van´t Hoff equation, both the molar enthalpy of reaction ΔrHm° and entropy of reaction ΔrSm° values were found to be positive for the two complexes, namely CmH2PO42+ and Cm(H2PO4)2+ [8].Relativistic quantum chemical investigations revealed a monodentate binding of the H2PO4- ligand to the central Cm3+ ion to be the most stable configuration for both complexes. By combining ab initio calculations with a thorough analysis of the obtained luminescence spectroscopic data, both CmH2PO42+ and Cm(H2PO4)2+ complexes with an overall CN of 9 were shown to be stable in solution at 25 °C. However, a different temperature-dependent evolution of the coordination of the Cm3+ ion to hydration water molecules could be derived from the electronic structure of the Cm(III)-phosphate complexes. More specifically, an overall coordination number of 9 was retained for the CmH2PO42+ complex in the investigated temperature range (25 to 90 °C), while a coordination change from 9 to 8 was established for the Cm(H2PO4)2+ species with increasing temperature [8]. This change of coordination upon increasing temperature, which has not been investigated in detail in the past, might also be relevant in the complexation of other f-elements with inorganic and/or organic ligands and deserves further exploration.[1] R. C. Ewing, Proc. Natl. Acad. Sci. USA 96, 3432 (1999).[2] D. Bregiroux et al., J. Nucl. Mater. 366, 52 (2007).[3] N. Huittinen et al., J. Nucl. Mater. 486, 148 (2017). [4] E. Du Fou de Kerdaniel, J. Nucl. Mater. 362, 451 (2007).[5] N. Huittinen et al., Inorg. Chem. 57, 6252−6265 (2018).[6] H. Moll et al., Radiochim. Acta, 99, 775−782 (2011).[7] N. Jordan et al., Inorg. Chem. 57, 7015-7024 (2018).[8] N. Huittinen et al., Inorg. Chem. 60, 10656−10673 (2021).[9] I. Grenthe et al., Second update on the chemical thermodynamics of uranium, neptunium, plutonium, americium and technetium, OECD Nuclear Energy Agency Data Bank, Eds., OECD Publications, Paris, France, (2020).
Published: 2022

36. Challenges in relativistic electronic structure calculations of gas-phase reactivity and thermodynamics of actinide species

Author: Vallet, Valérie, Réal, Florent, Severo Pereira Gomes, André, Kervazo, Sophie, Saab, Mohamad, Virot, François, Gong, Yu, Gibson, John K., Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Pôle Sûreté Nucléaire - Recherche en sûreté (IRSN/PSN-RES), Institut de Radioprotection et de Sûreté Nucléaire (IRSN), Chemical Sciences Division [LBNL Berkeley] (CSD), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), CPER CLIMIBIO, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille, PSN-RES, and ANR: 11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Probing the electronic structures, reactivity and thermodynamics properties of early actinide (U, Np, Pu) elements is a key fundamental aspect of actinide physical-chemistry, in order to elucidate to which extent their properties differ from one element to the other. When studied in the gas phase, it is possible to probe oxidation states that might not be readily accessible in condensed phase.In this presentation, we will first discuss the reactivity of pentavalent actinyl AnO2(V) sulfinate complexes [(AnVO2)(CH3SO2)2]- or [(AnVO2)(C6H5SO2)2]- to investigate on the one side how Np and Pu complexes might differ from U ones, and on the other side, how the relative strengths of C-S bond in methanesulfinate and benzesulftinate impact the fragmentation pathways. To answer these question, we have confronted the results of collision induced dissociation experiments to relativistic multi-reference electronic structure calculations [1].The second focus will be on the thermodynamics properties of gas-phase volatile plutonium species, PuO2, PuO3, and PuO2(OH)2, in their neutral and ionic forms. We showcase the use of relativistic quantum chemical methods to predict the forms and quantities of the released plutonium species under accidental conditions [2, 3].[1] V. Vallet, Y. Gong, M. Saab, F. Réal, J. K. Gibson, submitted to Dalton Trans.[2] K. Boguslawski, F. Réal, P. Tecmer, C. Duperrouzel, A. S. P. Gomes, Ö. Legeza, P. W. Ayers, and V. Vallet, Phys. Chem. Chem. Phys. 19, 4317 (2017)[3] S. Kervazo, F. Réal, F. Virot, A. S. P. Gomes, V. Vallet, Inorg. Chem. 58, 14507–14521 (2019).
Published: 2022

37. Surface spectroscopic analysis of aqueous phase iodine oxides : Electron binding energy and surface propensity

Author: Roose, Antoine, Opoku, Richard, Boucly, Anthony, Yang, Huanyu, Lezzi, Lucia, Toubin, Céline, Vallet, Valérie, Halbert, Loïc, Severo Pereira Gomes, André, Ammann, Markus, Artiglia, Luca, Laboratory of Environmental Chemistry [Villigen] (LUC), Paul Scherrer Institute (PSI), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institute of Atmospheric and Climate Science, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Iodine chemistry is implicated in atmospheric chemistry and can form several oxides such as HOI, I2, IO, OIO, and finally I2O5 or HIO3, which may nucleate as nanoparticles relevant for cloud formation in remote environments. These oxides can be formed through reaction with oxidants or other halogen compounds in the gas phase or the particle phase. Most of the iodide oxidation processes have been suggested to be enhanced at interfaces, similar to other halogen species, either due to the surface propensity of intermediates or the iodine species itself. However, no data are available about the surface concentration of iodine species other than iodide. After two decades of research into the surface propensity of iodide and bromide, the picture emerges that their surface propensity is not as extreme as initially thought. Liquid jet X-ray photoelectron spectroscopy (XPS) experiments have been carried out at the SIM beamline at the Swiss Light Source. Acquisition of kinetic energy dependent (thus at different probing depth) I3d, I4d core level and valence level spectra has been done for iodide, iodate and iodic acid. This allows to retrieve the surface propensity of these iodine species at the aqueous solution – air interface. Theoretical computations were performed to calculate the spectra using the so-called Frozen Embedding Method where DFT SAOP is coupled with CVS-EOM-IP-CCSD/d-aug-dy-all.ac2vz via a molecular mean-field X2C including the Gaunt interaction. The computation of the iodide core binding energies in the aqueous have been determined and compared to experimental measurements.
Published: 2022

38. Chemistry and speciation of protactinium – a first principles study

Author: Oher, Hanna, Vallet, Valérie, Maurice, Rémi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: National audience; It is of fundamental interest to understand and predict the chemistry of rare radioelements. In this work, we focus on protactinium (Z = 91), an element that is sandwiched in between thorium and uranium in the periodic table. Protactinium may naturally occur in environment (protactini-um-231 results from the decay of naturally occurring uranium-235) and also appear in thorium-based nuclear fuel cycles. From a chemical point of view, protactinium is a crossing point in the actinide series [1] and its chemistry is hard to predict [2,3]. We hypothesize that relativistic quantum chemistry should allow us to understand the enigmatic chemistry of protactinium and even predict it. For our first study, we have chosen to focus on the coordination sphere of protactinium and on the computation of equilibrium constants for experimentally known systems [3–5]. The occur-rence of 1:1, 1:2 and 1:3 complexes of protactinium(V) with sulfate and oxalate ligands is thus studied by means of quantum mechanical calculations, in particular based on density functional theory. The solvent effects, inherent to solution chemistry, are introduced by means of a polariz-able continuum model [6] and the explicit treatment of water molecules (micro solvation).The coordination sphere of protactinium has been obtained by geometry optimizations per-formed both in the gas phase and in solution. It involves an oxygen atom from the Pa=O mono-oxo bond and also oxygen atoms from the bidentate ligands, and in some cases from additional water molecules. The computation of equilibrium constants and comparison with experimental data is more subtle. First, only apparent constants were experimentally determined. Since the oc-currence of a mono-oxo bond was confirmed by EXAFS [5] even in the case of the 1:3 complex with oxalate ligands (corresponding to the stronger complexation), we hypothesize that this bond is also present in all the studied complexes. Second, number of explicitly treated water molecules should not be randomly chosen, it should ideally (i) lead to saturation of the coordination sphere of protactinium and (ii) be sufficient to stabilize the anionic ligands. We find that adding CN+1 water molecules is enough to satisfy both conditions in all the six studied complexes. By doing so and computing ligand-exchange equilibrium constants, we reproduce well the experimental trends for the exchange of 2 and 3 ligands, while the exchange of only one ligand (1:1 complex-es) is still hard to reproduce from computations.We report recent progress concerning the basic chemistry of protactinium. We have shown that its coordination sphere may include up to 8 oxygen atoms (from the original mono-oxo bond and from ligand and solvent molecule complexation) and find an approximate way of determin-ing trends in equilibrium constants, opening the way for future predictions.[1]Wilson R. et al. (2018) Nat. Commun. 9, 622.[2]Wilson R. (2012) Nat. Chem. 4, 586.[3]Le Naour C. et al. (2019) Radiochim. Acta, 107, 979-991.[4]Le Naour C. et al. (2005) Inorg. Chem. 44, 9542.[5]Mendes M. et al. (2010) Inorg. Chem. 49, 9962-9971.[6]Barone et al. (1997) J. Chem. Phys. 107, 3210-3221.
Published: 2022

39. Apports de la modélisation théorique à la radiochimie moléculaire

Author: Vallet, Valérie, Réal, Florent, Severo Pereira Gomes, André, Masella, Michel, Virot, François, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Service de Bioénergétique, Biologie Structurale et Mécanismes, Laboratoire Bioénergétique, Métalloprotéines et Stress, CEA, Université Paris-Saclay (CEA)-CEA, Université Paris-Saclay (CEA), Laboratoire d'étude de transfert des radioéléments (IRSN/PSN-RES/SAM/LETR), Service des Accidents Majeurs (IRSN/PSN-RES/SAM), Institut de Radioprotection et de Sûreté Nucléaire (IRSN)-Institut de Radioprotection et de Sûreté Nucléaire (IRSN), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: National audience; La radiochimie moléculaire se développe pour différents champs d’application, tels que la chimie fondamentale, l’environnement, la sûreté nucléaire ou encore la santé. Les calculs de structures électroniques ou de dynamique moléculaire permettent une compréhension fine des phénomènes physico-chimiques sous-jacents, et permettent d’interpréter et de prédire des données expérimentales. Dans cette présentation, nous décrirons les enjeux et les difficultés de la modélisation théorique. Nous illustrerons les avancées récentes sur les prédictions de rejets volatiles de plutonium lors d’accidents nucléaires [1 ], ou encore sur la complexation des actinides tétravalents en phase solvatée [2,3], la prédiction de données spectroscopiques de l’iode hydraté [4].[1 ] Kervazo, S.; Réal, F.; Virot, F.; Gomes, A. S. P.; Vallet, V. Inorg. Chem., 2019, 58, 14507–14521.[2] Banik, N. L.; Vallet, V.; Réal, F.; Belmécheri, R. M.; Schimmelpfennig, B.; Rothe, J.; Marsac, R.; Lindqvist-Reis, P.; Walther, C.; Denecke, M. A.; Marquardt, C. M. Dalton Trans., 2016, 45, 453–457.[3] Acher, E.; Réal, F.; Masella, M.; Vallet, V. Phys. Chem. Chem. Phys., 2020, 22, 2343–2350.[4] Bouchafra, Y.; Shee, A.; Réal, F.; Vallet, V.; Gomes, A. S. P. Phys. Rev. Lett., 2018, 121, 266001.
Published: 2022

40. The Atmospheric Oxidation of CH3I by the OH Radical: the Effect of Water Vapor

Author: Taamalli, Sonia, Infuso, Maxime, Amhani, Fatima, El Bakali, Abderrahman, Louis, Florent, Ribaucour, Marc, Duflot, Denis, Toubin, Céline, Cernusak, Ivan, Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 (PC2A), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and Comenius University in Bratislava
Subjects: [CHIM]Chemical Sciences
Abstract: International audience
Published: 2022

41. A Molecular Scale Investigation of Organic/Inorganic Ion Selectivity at the Air–Liquid Interface

Author: Ozge Ozgurel, Denis Duflot, Michel Masella, Florent Réal, Céline Toubin, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Biologie Structurale et Radiobiologie (LBSR), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), (Grants DARI x2016081859 and A0050801859), French research network GDR 2035 SolvATE., CLIMIBIO, ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), and ANR-16-IDEX-0004,ULNE,ULNE(2016)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Atmospheric Science, Space and Planetary Science, Geochemistry and Petrology, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Aerosol particles are known to have a major impact on the climate by directly absorbing and scattering solar radiation and indirectly by acting as cloud condensation nuclei. The main contribution to aerosol emission comes from the ocean through the production of sea spray aerosols (SSA), which consist of organic and inorganic species, formed in different sizes and shapes, depending on their mixing ratios. The chemical composition of those SSA will be naturally impacted by the chemical composition of the air/water interface. Through complex experiments, it has been shown how surface activity impacts the selective transfer of species from solution to the aerosol phase. While experiments offer a general picture, it is interesting to probe the properties through a systematic and decoupled approach at the molecular level. The present study provides indeed theoretical results to be confronted to reported experimental observations by means of molecular level simulations. We chose a series of linear mono- and dicarboxylates (containing 4, 6, or 8 carbon atoms) being identified as a large fraction of the SSA surface composition, with the possible counterions (Na+, K+, Ca2+, Mg2+). Classical molecular dynamics is employed to model the distribution of these ions in a water slab using an ab initio based polarizable force-field model. These calculations allow us to derive some trends on the enrichment of inorganic and organic ions at the liquid–air interface compared to their eventual partitioning in the bulk phase. Indeed, medium to long chain mono- or dicarboxylates predominantly remain at the surface of the aerosol, with inorganic cations accumulating underneath, neutralizing the surface charge. For shorter chains, solvation in the bulk appears more favorable. K+ and the dications show a strong ion pairing with the organics, this ion pairing driving their surface vs bulk distribution. In addition, surface tension has been evaluated for the long chain, i.e., having 8 carbons, mono- and dicarboxylates in the presence of the various cations. The surface propensity of the organic chains leads in general to a reduction of surface tension compared to neat water, while mixtures of dicarboxylates and dications give higher values. Finally, these outcomes are discussed in comparison with previous work and within the context of SSA chemistry.
Published: 2022

42. Final-state-resolved mutual neutralization in I+ - I− collisions

Author: Poline, Mathias, Yuan, Xiang, Badin, Sylvain, Ji, Mingchao, Rosén, Stefan, Indrajith, Suvasthika, Thomas, Richard D, Schmidt, Henning, Zettergren, Henning, Severo Pereira Gomes, André, Sisourat, Nicolas, Department of Physics [Stockholm], Stockholm University, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Vrije Universiteit Amsterdam [Amsterdam] (VU), Laboratoire de Chimie Physique - Matière et Rayonnement (LCPMR), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Theoretical Chemistry, ANR-16-IDEX-0004,ULNE,ULNE(2016), Department of Theoretical Chemistry and Amsterdam Centre for Multiscale Modeling (ACMM) VU University Amsterdam (ACMM), MESONM International Associated Laboratory (LAI, Grant No. ANR-16-IDEX-0004), French national supercomputing facilities (Grant No. DARI A0090801859), DESIREE (Swedish Research Council Contracts No. 2017-00621 and No. 2021-00155), Project 'Probing charge- and mass- transfer reactions on the atomic level,' supported by the Knut and Alice Wallenberg Foundation (Grant No. 2018.0028), COST Action (CA18212)-Molecular Dynamics in the GAS phase (MD- GAS), supported by COST (European Cooperation in Science and Technology)., Swedish Research Council (Contracts No. 2018-04092 and No. 2020-03437), This material is based upon work supported by the Air Force Office of Scientific Research under Award No. FA9550-19-1-7012 (R.D.T.)., and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS]Physics [physics]/Physics [physics], [CHIM]Chemical Sciences, SDG 7 - Affordable and Clean Energy
Abstract: International audience; We have studied the mutual neutralization reaction of atomic iodine ions (i.e., I++I−→I+I) in a cryogenic double electrostatic ion-beam storage-ring apparatus. Our results show that the reaction forms iodine atoms either in the ground-state configuration (I(5p5 2P0), ∼40%) or with one atom in an electronically excited state (I(6s2 [2]), ∼60%), with no significant variation over the branching ratios in the studied collision-energy range (0.1–0.8 eV). We estimate the total charge-transfer cross section to be of the order of 10-13cm2 at 0.1 eV collision energy. Ab initio relativistic electronic structure calculations of the potential-energy curves of I2 suggest that the reaction takes place at short internuclear distances. The results are discussed in view of their importance for applications in electric thrusters.
Published: 2022

43. Valence shell direct double photodetachment in polyanions

Author: Alexandre Giuliani, Philippe Dugourd, Rodolphe Antoine, Laurent Nahon, Denis Duflot, Claire Brunet, Francis Canon, Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Centre des Sciences du Goût et de l'Alimentation [Dijon] (CSGA), Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Département Caractérisation et Elaboration des Produits Issus de l'Agriculture (CEPIA), Institut National de la Recherche Agronomique (INRA), ANR 08-BLAN-0065 + 2012-088620, Institut des Sciences Analytiques (ISA), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-École normale supérieure - Lyon (ENS Lyon), Centre National de la Recherche Scientifique (CNRS)-AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Institut National de la Recherche Agronomique (INRA)-Université de Bourgogne (UB), Institut Lumière Matière [Villeurbanne] ( ILM ), Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Analytiques ( ISA ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Physico-Chimie Moléculaire Théorique ( PCMT ), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 ( PhLAM ), Université de Lille-Centre National de la Recherche Scientifique ( CNRS ) -Université de Lille-Centre National de la Recherche Scientifique ( CNRS ), Centre des Sciences du Goût et de l'Alimentation [Dijon] ( CSGA ), Institut National de la Recherche Agronomique ( INRA ) -Université de Bourgogne ( UB ) -AgroSup Dijon - Institut National Supérieur des Sciences Agronomiques, de l'Alimentation et de l'Environnement-Centre National de la Recherche Scientifique ( CNRS ), Synchrotron SOLEIL ( SSOLEIL ), Centre National de la Recherche Scientifique ( CNRS ), Département Caractérisation et Elaboration des Produits Issus de l'Agriculture ( CEPIA ), and Institut National de la Recherche Agronomique ( INRA )
Subjects: mass spectrometry, synchrotron radiation, valence shell, photoionization, vuv radiation, vuv, protein, General Physics and Astronomy, Synchrotron radiation, Photoionization, 010402 general chemistry, 01 natural sciences, Ab initio quantum chemistry methods, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Food and Nutrition, Physics::Atomic Physics, Physics::Chemical Physics, Physics, 010304 chemical physics, Relaxation (NMR), 0104 chemical sciences, [ PHYS.PHYS.PHYS-CHEM-PH ] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Alimentation et Nutrition, Ion trap, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Atomic physics, Absorption (chemistry), Valence electron, Excitation
Abstract: Funding Agency: Agence Nationale de la Recherche Scientifique, France = 08-BLAN-0065 + GENCI-CINES = 2012-088620; International audience; A valence shell study of electrosprayed insulin protein polyanion photodetachment was carried out on a vacuum ultra-violet synchrotron radiation beamline coupled to a radiofrequency ion trap, for both close- and open-shell species. A two-electron photodetachment is observed, which arises from two different mechanisms that are disentangled: a sequential multi-photon absorption and a direct one-photon two-electron process. The threshold for the direct double-electron ejection is measured at 11.4 eV and corresponds to electronic excitation in the valence shell, which makes it the first observation of direct double photodetachment in the valence shell. The results are discussed in the light of previous knowledge from multiple photoionization and ab initio calculations on model polyanions. Double photodetachment appears to be a relaxation mechanism that leads to oxidized anions of striking stability, a feature of high relevance in radiobiology.
Published: 2013

44. Structure–Property Relationships in Photoluminescent Bismuth Halide Organic Hybrid Materials

Author: Karah E. Knope, R. Lee Ayscue, Florent Réal, Jeffery A. Bertke, Valérie Vallet, Department of Chemistry, Georgetown University [Washington] (GU), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Clare Boothe Luce Foundation (K.E.K.), DoD SMART Scholarship Program, Ministry of Higher Education and Research, Hauts de France Council and European Regional Development Fund (ERDF) through the Contrat de Projets état-Région (CPER-CLIMIBIO), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), and Department of Chemistry [Washington]
Subjects: Aqueous solution, Photoluminescence, Chemistry, Ligand, Doping, chemistry.chemical_element, Halide, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Bismuth, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Monomer, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, 0210 nano-technology, Hybrid material
Abstract: International audience; Seven novel bismuth(III)-halide phases, Bi2Cl6(terpy)2·0.5(H2O) (1), Bi2Cl4(terpy)2(k2-TC)2(2) (TC = 2-thiophene monocarboxylate), BiCl(terpy)(k2-TC)2 (3A-Cl), BiBr(terpy)(k2-TC)2 (3A-Br), BiCl(terpy)(k2-TC)2 (3B-Cl), [BiCl(terpy)(k2-TC)2][Bi(terpy)(k2-TC)3]·0.55(TCA) (4), [BiBr3(terpy)(MeOH)] (5), and [BiBr2(terpy)(k2-TC)][BiBr1.16(terpy)(k2-TC)1.84] (6), were prepared under mild synthetic conditions from methanolic/aqueous solutions containing BiX3 (X = Cl, Br) and 2,2′:6′,2″-terpyridine (terpy) and/or 2-thiophene monocarboxylic acid (TCA). A heterometallic series, 3A-Bi1–xEuxCl, with the general formula Bi1–xEuxCl(terpy)(k2-TC)2 (x = 0.001, 0.005, 0.01, 0.05) was also prepared through trace Eu doping of the 3A-Cl phase. The structures were determined through single-crystal X-ray diffraction and are built from a range of molecular units including monomeric and dimeric complexes. The solid-state photoluminescent properties of the compounds were examined through steady-state and time-resolved methods. While the homometallic phases exhibited broad green to yellow emission, the heterometallic phases displayed yellow, orange, and red emission that can be attributed to the simultaneous ligand/Bi-halide and Eu centered emissions. Photoluminescent color tuning was achieved by controlling the relative intensities of these concurrent emissions through compositional modifications including the Eu doping percentage. Notably, all emissive homo- and heterometallic phases exhibited rare visible excitation pathways that based on theoretical quantum mechanical calculations are attributed to halide-metal to ligand charge transfer (XMLCT). Through a combined experimental and computational approach, fundamental insight into the structure–property relationships within these Bi halide organic hybrid materials is provided.
Published: 2021

45. Exploring excited state potential energy profile and luminescence properties of uranyl-based complexes by TRLFS and ab initio method

Author: Vallet, Valérie, Oher, Hanna, Réal, Florent, Vercouter, Thomas, Severo Pereira Gomes, André, Wilson, Richard, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Service d'études analytiques et de réactivité des surfaces (SEARS), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Chemical Sciences and Engineering Division [Argonne], Argonne National Laboratory [Lemont] (ANL), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, and ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Uranyl complexes have been the subject of many research works for fundamental chemistry of actinides, environmen-tal issues, or nuclear fuel cycle processes. The formation of various uranyl complexes, with organic and inorganic ligands in solution must be characterized for a better understanding of U(VI) speciation. As uranyl-ligand interactions and the symmetry of the complexes affect the electronic structure of U(VI) and thus its luminescence properties, time-resolved laser induced fluorescence spectroscopy (TRLFS) is one of the major techniques to characterize U(VI) com-plexes, with high sensitivity and selectivity. However, most of the relevant systems have complex chemical composi-tion in solution and the identification of each species from spectroscopic data is challenging.In our study, the synergy between TRLFS and ab initio-based interpretation appears as a promising route for com-plexation data. Luminescence spectra of uranyl complexes in solution show in general a narrow energetical range about 6000 cm-1 and we can identify a single electronic transition between the initial and target states with the vibrationally resolved band [1]. The main challenge consists in exploiting a computationally cheap and effective theoretical ap-proach, in a relativistic context, to characterize the main spectral parameters of the ground and luminescent states of symmetrical uranyl compounds (i.e. UO2Cl42-, UO2F53-, UO2(CO3)34-, UO2(NO3)L2) with different organic or inorganic counter ions after the photo-excitation. We will illustrate that TD-DFT with the CAM-B3LYP functional is able to provide accurate excitation/emission energies for these systems, together with accurate vibronic progressions allowing the assignment of experimental data.As a benchmark system serving the purpose of assessing the accuracy of our theoretical protocol, the uranyl tetrachloride UO2Cl42- was selected because of the extensive amount of structural and spectroscopic data available [2]. A good agreement was found between ours and previously obtained theoretical data (structural parameters, orbitals nature, excitation energies) [3]; the final luminescence spectrum is in remarkable agreement with our TRLFS measurements [4]. We will also quantify the effects of organic or inorganic counterions [5, 6], along with that of first-sphere ligands that might perturb the uranyl(VI) moiety.This work showcases how one can predict vibrationally resolved spectra to assign the recorded TRLFS data, and shed light on the relationship between the uranyl coordination and its luminescence properties.
Published: 2022

46. Chemistry, spectroscopy and speciation of protactinium

Author: Oher, Hanna, Vallet, Valérie, Maurice, Rémi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-21-CE29-0027,CHESS,Chimie, spectroscopie et spéciation du protactinium(2021)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2022

47. Quantum chemical investigation of intramolecular hydrogen bonds in oxygenated aromatic molecules: influence of ring size, donor/acceptor groups and substituants

Author: Bruckhuisen, Jonas, Gomez Pech, Cecilia, Vallet, Valérie, Olejniczak, Małgorzata, Cuisset, Arnaud, Goubet, Manuel, Dhont, Guillaume, Laboratoire de Physico-Chimie de l'Atmosphère (LPCA), Université du Littoral Côte d'Opale (ULCO), Center of New Technology warsaw, Warsaw University of Technology [Warsaw], Physique Moléculaire aux Interfaces (PMI), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physico-Chimie Moléculaire Théorique (PCMT), Centre of New Technologies, University of Warsaw (UW), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Hydrogen bonds (HBs) are important for a broad range of applications and play a fundamental role in structural chemistry and biology. HB interactions, dynamics and their directionality are discussed for al- most one century and there is still a need for further experiments and theoretical investigations to fully encompass this complex interaction. Especially the experimental investigation of weak intramolecular HBs of isolated molecules in the gas phase remains challenging. Quantum chemical tools are needed to support high resolution THz and IR spectroscopies which can reveal the influence of intramolecular HBs on the rovibrational dynamics[1]. In this work we focus on intramolecular HBs of oxygenated aromatic mo- lecules. They are investigated through a combination of quantum theory of atoms in molecules QTAIM[2], non-covalent interactions NCI[3], natural bond orbitals NBO[4], and topological data analysis TDA[5]. We studied the influence of the substitutants, of the donor or acceptor groups and of the number of atoms in- cluded in the ring formed by the HB. We relate our findings with recent rovibrational measurements in catechol (1,2-dihydroxybenzene) and guaiacol. We provide an overview of the problems arising while studying weak intramolecular HBs stabilizing oxygenated aromatic compounds and we discuss the performance of the different quantum chemical tools.[1] J. Bruckhuisen, Molecules, 26, 3645, (2021).[2] R. Bader, International series of monographs on chemistry, 22, (1994).[3] C. Narth, Challenges and advances in computational chemistry and physics, 491-527, (2016). [4] E. Glendening, NBO 6.0, (2013).[5] N. Otter, EPJ Data Sci., 6, 17, (2017).
Published: 2022

48. Molecular dynamics investigation of the influence of surfactants on halogens propensity at the air-water interface

Author: Abouhaidar, Rawan, Toubin, Céline, Duflot, Denis, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; In the atmospheric environment, both organic and inorganic compounds are present and have a strong influence on the chemical composition of the troposphere. On the other side, the ocean surface water and sea mist spray are enriched with surface active organic compounds, which may have a significant effect on the distribution of halide ions at the interface [1,2]. For instance, the abundance of bromide (Br-) ions at the interface is implicated in halogen activation processes relevant for the ozone budget in the troposphere [3]. In this context, we evaluate the surface affinity of cationic hexylammonium, neutral hexylamine, and anionic propylsulfate at the air/liquid interface, and the effect of these ionic surfactants on the abundance of bromide at interfaces. Inspired by liquid X-ray Photoelectron Spectroscopy (XPS) experiments, we conducted Molecular Dynamics (MD) simulations and we were able to speculate about the distribution of these species between bulk and surface area in aqueous systems. Here, the results are in good agreement with the experimental ones, which clearly advocate that those organic molecules dislike the bulk and prefer to reside near the free surface; indicating the effect of salting. In contrast, both solutions containing hexylammonium and hexylamine show an enhancement of the surfactant bromide concentration while the propylsulfate solution do not alter the bromide concentration. In parallel, the same results were observed in the presence of NaCl. These results demonstrate that molecular level properties bring valuable insights on the interfacial behavior of organic and inorganic species on water films, that can be transposed to aerosol particles.
Published: 2022

49. Assessing MP2 frozen natural orbitals in relativistic correlated electronic structure calculations

Author: Andre Severo Pereira Gomes, Lucas Visscher, Xiang Yuan, Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam [Amsterdam] (VU), French national supercomputing facilities (grant DARI A0090801859), ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011), ANR-16-IDEX-0004,ULNE,ULNE(2016), Theoretical Chemistry, AIMMS, Vallet, Valérie, Physiques et Chimie de l'Environnement Atmosphérique - - Cappa2011 - ANR-11-LABX-0005 - LABX - VALID, ULNE - - ULNE2016 - ANR-16-IDEX-0004 - IDEX - VALID, Department of Theoretical Chemistry and Amsterdam Centre for Multiscale Modeling (ACMM) VU University Amsterdam (ACMM), and ANR-19-CE29-0019,CompRIXS,Calcul de la diffusion inélastique résonante de rayons X pour toute la classification périodique(2019)
Subjects: Chemical Physics (physics.chem-ph), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Physics - Chemical Physics, General Physics and Astronomy, FOS: Physical sciences, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], SDG 7 - Affordable and Clean Energy, Physical and Theoretical Chemistry, [PHYS.PHYS.PHYS-CHEM-PH] Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: The high computational scaling with the number of correlated electrons and the size of the basis set is a bottleneck which limits applications of coupled cluster (CC) algorithms. This is particularly so for calculations based on 2- or 4-component relativistic Hamiltonians, which often employ uncontracted basis sets and lead to large virtual molecular orbital (VMO) spaces. This problem may be alleviated by employing a more compact set of virtual spinors than those provided by the canonical Hartree-Fock (HF) set, such as those based on natural orbitals (NOs). In this paper we describe the implementation of a module for generating NOs for correlated wavefunctions, and in particular MP2 frozen natural orbitals (MP2FNOs), as a component of our novel implementation of relativistic coupled cluster theory for massively parallel architectures [J. Pototschnig et. al., J. Chem. Theory Comput. 17, 5509, 2021]. Our implementation is capable of manipulating both complex and quaternion density matrices, thus allowing for the generation of both Kramers-restricted and Kramers-unrestricted MP2FNOs. Furthermore, NOs are re-expressed in the parent atomic orbital (AO) basis, so that the code also makes it possible to generate CCSD natural orbitals in AO basis for further analysis. By investigating the truncation errors of MP2FNOs for both the correlation energy and molecular properties at CCSD level such as the electric field gradients at the nuclei (EFGs), electric dipole and quadrupole moments for hydrogen halides HX (X=F-Ts), and parity-violating energy differences (PV) for H$_2$Y$_2$ (Y=O-Se), we find that MP2FNOs accelerate the convergence of the correlation energy in a roughly uniform manner across the periodic table and that, with VMO spaces truncated to around half the size of the full spaces ones, it is possible to obtain reliable estimates for both energies and all molecular properties considered., Comment: 16 pages, 9 figures
Published: 2022

50. IO radical yields from iodide oxidation by ozone at aerosol proxy surfaces

Author: Antoine, Roose, Finkenzeller, Henning, Réal, Florent, Vallet, Valérie, Toubin, Céline, Gyrin, S., Lezzi, L., Volkamer, Rainer, Ammann, Markus, Laboratory of Environmental Chemistry [Villigen] (LUC), Paul Scherrer Institute (PSI), Physico-Chimie Moléculaire Théorique (PCMT), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Biochemistry [Boulder], University of Colorado [Boulder], Institute of Atmospheric and Climate Science, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), ANR-16-IDEX-0004,ULNE,ULNE(2016), and ANR-11-LABX-0005,Cappa,Physiques et Chimie de l'Environnement Atmosphérique(2011)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Recently, Koenig et al. [1] measured both gas phase iodine species and particulate iodine (iodate and iodide) in the lower stratosphere indicating that tropospheric multiphase redox reactions prevent poorly soluble gaseous iodine species from removal by wet deposition leading to injections of inorganic iodine into the lower stratosphere. This may influence stratospheric ozone depletion both indirectly through activation of iodide to molecular halogens and directly through the aqueous phase reaction of ozone (O3) with iodide [2]. The bulk aqueous phase kinetics of this reaction have been reasonably well established for dilute solutions, though over a too narrow temperature range only [3,4]. The product of this reaction, IO-, is reacting with I- to I2(g) under most circumstances. Sakamoto et al. [3] have suggested that in addition IO(g), may be formed. The primary reaction of iodide with O3 depends on pH. Solute strength effects and the extent of a surface reaction have not been sufficiently established [3,5]. The objectives of this work is to determine the temperature dependence of the oxidation of iodide by ozone as well as to have a better understanding of the parameters that lead to IO radical and I2 formation. In this study, we used a trough reactor [6] coupled to Cavity Enhanced – Differential Optical Absorption Spectroscopy (CE-DOAS) [7] in order to study the reactivity in the range of temperatures from 255.15 to 291.15 K, in dilute aqueous solution and concentrated ammonium sulfate solutions. Preliminary results show that the IO/I2 ratio is in the range of 10-3 – 10-2. While I2 formation seems to be a bulk aqueous phase process, IO formation seems to result predominantly from a surface process. These experiments are also compared with molecular modeling investigations (ONIOM QM/MM method), where the energy barrier of the primary reaction is determined in the aerosol phase.References[1]T. K. Koenig et al., PNAS, 117, 4 (2020). [2]L. J. Carpenter et al., Nat. Geosci., 6 (2013).[3]Y. Sakamoto et al., J. Phys. Chem. A, 113, 27 (2009).[4]L. Magi et al., J. Phys. Chem. A, 101 (1997)[5]C. Moreno et al., Phys. Chem. Chem. Phys., 22 (2020)[6]L. Artiglia et al., Nat. Commun., 8 (2017)[7]M. Wang et al., Atmos. Meas. Tech., 14, (2021).
Published: 2022

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