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Your search keyword '"Sergentu, Dumitru‐Claudiu"' showing total 201 results
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201 results on '"Sergentu, Dumitru‐Claudiu"'

1. The resolution of the weak-exchange limit made rigorous, simple and general in binuclear complexes

Author

Sergentu, Dumitru-Claudiu, Guennic, Boris Le, and Maurice, Rémi

Subjects
Physics - Chemical Physics
Abstract

The correct interpretation of magnetic properties in the weak-exchange regime has remained a challenging task for several decades. In this regime, the effective exchange interaction between local spins is quite weak, of the same order of magnitude or smaller than the various anisotropic terms, which generates a complex set of levels characterized by spin spin mixing. Although the model multispin Hamiltonian in the absence of local orbital momentum, \hms{} = \js{} + \da{} +\db{} + \dab{}, is considered good enough to map the experimental energies at zero field and in the strong-exchange limit, theoretical works pointed out limitations of this simple model. This work revives the use of \hms{} from a new theoretical perspective, detailing point-by-point a strategy to correctly map the computational energies and wave functions onto \hms{} , thus validating it regardless of the exchange limit. We will distinguish two cases, based on experimentally characterized dicobalt(II) complexes from the literature. If centrosymmetry imposes alignment of the various rank-2 tensors constitutive of \hms{} in the first case, the absence of any symmetry element prevents such alignment in the second case. In such a context, the strategy provided herein becomes a powerful tool to rationalize the experimental magnetic data, since it is capable of fully and rigorously extracting the multispin model without any assumption on the orientation of its constitutive tensors. Furthermore, the strategy allows to question the use of the spin Hamiltonian approach by explicitly controlling the projection norms on the model space, which is showcased in the second complex where local orbital momentum could have occurred (distorted octahedra). Finally, previous theoretical data related to a known dinickel(II) complex is reinterpreted, clarifying initial wanderings regarding the weak exchange limit.

Published
2023

2. Chemical design of electronic and magnetic energy scales of tetravalent praseodymium materials

Author

Ramanathan, Arun, Kaplan, Jensen, Sergentu, Dumitru-Claudiu, Branson, Jacob A, Ozerov, Mykhaylo, Kolesnikov, Alexander I, Minasian, Stefan G, Autschbach, Jochen, Freeland, John W, Jiang, Zhigang, Mourigal, Martin, and La Pierre, Henry S

Abstract

Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the tetravalent oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+-oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f1 configuration with ligand valence electrons, analogous to transition metals. The competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the Jeff = 1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials.

Published
2023

3. Chemical Design of Electronic and Magnetic Energy Scales in Tetravalent Praseodymium

Author

Ramanathan, Arun, Kaplan, Jensen, Sergentu, Dumitru-Claudiu, Branson, Jacob A., Ozerov, Mykhaylo, Kolesnikov, Alexander I., Minasian, Stefan G., Autschbach, Jochen, Freeland, John W., Jiang, Zhigang, Mourigal, Martin, and La Pierre, Henry S.

Subjects
Condensed Matter - Materials Science, Condensed Matter - Strongly Correlated Electrons
Abstract

Lanthanides in the trivalent oxidation state are typically described using an ionic picture that leads to localized magnetic moments. The hierarchical energy scales associated with trivalent lanthanides produce desirable properties for e.g., molecular magnetism, quantum materials, and quantum transduction. Here, we show that this traditional ionic paradigm breaks down for praseodymium in the 4+ oxidation state. Synthetic, spectroscopic, and theoretical tools deployed on several solid-state Pr4+ oxides uncover the unusual participation of 4f orbitals in bonding and the anomalous hybridization of the 4f1 configuration with ligand valence electrons, analogous to transition metals. The resulting competition between crystal-field and spin-orbit-coupling interactions fundamentally transforms the spin-orbital magnetism of Pr4+, which departs from the Jeff =1/2 limit and resembles that of high-valent actinides. Our results show that Pr4+ ions are in a class on their own, where the hierarchy of single-ion energy scales can be tailored to explore new correlated phenomena in quantum materials., Comment: 9 pages, 4 figures, and SI (47 pages)

Published
2022
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4. Correction: Enhanced 5f-δ bonding in [U(C 7 H 7 ) 2 ] − : C K-edge XAS, magnetism, and ab initio calculations

Author

Qiao, Yusen, Ganguly, Gaurab, Booth, Corwin H, Branson, Jacob A, Ditter, Alexander S, Lussier, Daniel J, Moreau, Liane M, Russo, Dominic R, Sergentu, Dumitru-Claudiu, Shuh, David K, Sun, Taoxiang, Autschbach, Jochen, and Minasian, Stefan G

Subjects
Chemical Sciences, Theoretical and Computational Chemistry, Organic Chemistry, Chemical sciences, Engineering
Abstract

Correction for 'Enhanced 5f-δ bonding in [U(C7H7)2]-: C K-edge XAS, magnetism, and ab initio calculations' by Yusen Qiao et al., Chem. Commun., 2021, 57, 9562-9565, DOI: 10.1039/D1CC03414F.

Published
2021

5. Enhanced 5f-δ bonding in [U(C7H7)2]-: C K-edge XAS, magnetism, and ab initio calculations.

Author

Qiao, Yusen, Ganguly, Gaurab, Booth, Corwin H, Branson, Jacob A, Ditter, Alexander S, Lussier, Daniel J, Moreau, Liane M, Russo, Dominic R, Sergentu, Dumitru-Claudiu, Shuh, David K, Sun, Taoxiang, Autschbach, Jochen, and Minasian, Stefan G

Subjects
Chemical Sciences, Organic Chemistry
Abstract

5f covalency in [U(C7H7)2]- was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results revealed U 5f orbital participation in δ-bonding in both the ground- and core-excited states; additional 5f ϕ-mixing is observed in the core-excited states. Comparisons with U(C8H8)2 show greater δ-covalency for [U(C7H7)2]-.

Published
2021

6. Synthesis, Characterization, and Electrochemistry of the Homoleptic f Element Ketimide Complexes [Li]2[M(NC t BuPh)6] (M = Ce, Th)

Author

Assefa, Mikiyas K, Sergentu, Dumitru-Claudiu, Seaman, Lani A, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W

Subjects
Inorganic Chemistry, Chemical Sciences, Physical Chemistry (incl. Structural), Other Chemical Sciences, Inorganic & Nuclear Chemistry, Inorganic chemistry, Macromolecular and materials chemistry
Abstract

Reaction of [Ce(NO3)3(THF)4] with 6 equiv of Li(N═CtBuPh), followed by addition of 0.5 equiv of I2, affords the homoleptic Ce(IV) ketimide [Li]2[Ce(N═CtBuPh)6] (1), which can be isolated in 44% yield after workup. Similarly, reaction of [ThCl4(DME)2] (DME = 1,2-dimethoxyethane) with 6 equiv of Li(N═CtBuPh) in tetrahydrofuran affords the isostructural Th(IV) ketimide [Li]2[Th(N═CtBuPh)6] (2), which can be isolated in 53% yield after workup. Both 1 and 2 were fully characterized, including analysis by X-ray crystallography, allowing for a detailed structural and spectroscopic comparison. The electronic structures of 1 and 2 were also explored with density functional theory and multiconfigurational wave function calculations. Additionally, the redox chemistry of 1 was probed by cyclic voltammetry, which revealed a highly cathodic Ce(IV)/Ce(III) reduction potential, providing evidence for the ability of the ketimide ligand to stabilize high oxidation states of the lanthanides.

Published
2019

7. Synthesis, Characterization, and Electrochemistry of the Homoleptic f Element Ketimide Complexes [Li]2[M(N═CtBuPh)6] (M = Ce, Th).

Author

Assefa, Mikiyas K, Sergentu, Dumitru-Claudiu, Seaman, Lani A, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W

Subjects
Inorganic & Nuclear Chemistry, Inorganic Chemistry, Physical Chemistry (incl. Structural), Other Chemical Sciences
Abstract

Reaction of [Ce(NO3)3(THF)4] with 6 equiv of Li(N═CtBuPh), followed by addition of 0.5 equiv of I2, affords the homoleptic Ce(IV) ketimide [Li]2[Ce(N═CtBuPh)6] (1), which can be isolated in 44% yield after workup. Similarly, reaction of [ThCl4(DME)2] (DME = 1,2-dimethoxyethane) with 6 equiv of Li(N═CtBuPh) in tetrahydrofuran affords the isostructural Th(IV) ketimide [Li]2[Th(N═CtBuPh)6] (2), which can be isolated in 53% yield after workup. Both 1 and 2 were fully characterized, including analysis by X-ray crystallography, allowing for a detailed structural and spectroscopic comparison. The electronic structures of 1 and 2 were also explored with density functional theory and multiconfigurational wave function calculations. Additionally, the redox chemistry of 1 was probed by cyclic voltammetry, which revealed a highly cathodic Ce(IV)/Ce(III) reduction potential, providing evidence for the ability of the ketimide ligand to stabilize high oxidation states of the lanthanides.

Published
2019

8. Use of 15 N NMR spectroscopy to probe covalency in a thorium nitride

Author

Staun, Selena L, Sergentu, Dumitru-Claudiu, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W

Subjects
Inorganic Chemistry, Chemical Sciences, Chemical sciences
Abstract

Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d 8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th-Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th-NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]- vs. comparable thorium imido and oxo complexes.

Published
2019

9. Use of 15N NMR spectroscopy to probe covalency in a thorium nitride.

Author

Staun, Selena L, Sergentu, Dumitru-Claudiu, Wu, Guang, Autschbach, Jochen, and Hayton, Trevor W

Subjects
Chemical Sciences
Abstract

Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d 8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th-Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th-NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]- vs. comparable thorium imido and oxo complexes.

Published
2019

12. A diuranium carbide cluster stabilized inside a C80 fullerene cage.

Author

Zhang, Xingxing, Li, Wanlu, Feng, Lai, Chen, Xin, Hansen, Andreas, Grimme, Stefan, Fortier, Skye, Sergentu, Dumitru-Claudiu, Duignan, Thomas J, Autschbach, Jochen, Wang, Shuao, Wang, Yaofeng, Velkos, Giorgios, Popov, Alexey A, Aghdassi, Nabi, Duhm, Steffen, Li, Xiaohong, Li, Jun, Echegoyen, Luis, Schwarz, WH Eugen, and Chen, Ning

Abstract

Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing Ih(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

Published
2018

14. The Counterintuitive Relationship between Orbital Energy, Orbital Overlap, and Bond Covalency in CeF62–and CeCl62–

Author

Branson, Jacob A., Smith, Patrick W., Sergentu, Dumitru-Claudiu, Russo, Dominic R., Gupta, Himanshu, Booth, Corwin H., Arnold, John, Schelter, Eric J., Autschbach, Jochen, and Minasian, Stefan G.

Abstract

The 4f orbitals of Ce(IV) have shown appreciably enhanced covalent mixing with ligand orbitals relative to those of Ce(III). Here, X-ray spectroscopy, magnetic susceptibility measurements, and theoretical methods are used to investigate 4f covalency in CeF62–and CeCl62–. These techniques show covalent mixing between Ce 4f and F 2p orbitals to be about 25% less than mixing between Ce 4f and Cl 3p orbitals, placing CeF62–among the most ionic Ce(IV) compounds to-date. However, ligand field analysis using the experimental data shows significantly higher 4f orbital overlap with the F 2p orbitals compared to the Cl 3p. This result is counterintuitive since the Ce–F bonds display less 4f covalency despite their higher orbital overlap, and greater overlap is traditionally associated with enhanced bond covalency. The weaker covalency is attributed to the large energy gap between Ce 4f and F 2p orbitals strongly counteracting the higher orbital overlap. These results highlight that only a concerted consideration of both atomic orbital overlap and energy matching in f-element systems leads to an accurate picture of their bonding.

Published
2024
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15. The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

Author

Fundación la Caixa, European Commission, Ministerio de Ciencia e Innovación (España), Department of Energy (US), Swiss National Science Foundation, Ministero dell'Istruzione, dell'Università e della Ricerca, Carl Trygger Foundation, Royal Society (UK), Independent Research Fund Denmark, German Research Foundation, Generalitat de Catalunya, Olle Engkvist Foundation, National Centre for Research and Development (Poland), National Science Foundation (US), Academy of Finland, Knut and Alice Wallenberg Foundation, Swedish Research Council, Université de Nantes, Japan Society for the Promotion of Science, Università degli Studi di Siena, Novo Nordisk Foundation, Argonne National Laboratory (US), National University of Singapore, Air Force Office of Scientific Research (US), Linköping University, Centre National de la Recherche Scientifique (France), Li Manni, Giovanni [0000-0002-3666-3880], Fdez Galván, Ignacio [0000-0002-0684-7689], #NODATA#, Aleotti, Flavia [0000-0002-7176-5305], Aquilante, Francesco [0000-0003-4422-3938], Autschbach, Jochen [0000-0001-9392-877X], Avagliano, Davide [0000-0001-5539-9731], Baiardi, Alberto [0000-0001-9112-8664], Bao, Jie J. [0000-0003-0197-3405], Battaglia, Stefano [0000-0002-5082-2681], Blanco-González, Alejandro [0000-0001-7379-2588], Bokarev, Sergey I. [0000-0003-0779-5013], Broer, Ria [0000-0002-5437-9509], Cacciari, Roberto [0000-0001-8290-4297], Calio, Paul B. [0000-0001-8385-2628], Carlson, Rebecca K. [0000-0002-1710-5816], Carvalho Couto, Rafael [0000-0003-4020-0923], Cerdán, L. [0000-0002-7174-2453], Chibotaru, Liviu F. [0000-0003-1556-0812], Chilton, Nicholas F. [0000-0002-8604-0171], Church, Jonathan Richard [0000-0001-5986-1305], Conti, Irene [0000-0001-7982-4480], Coriani, Sonia [0000-0002-4487-897X], Cuéllar-Zuquin, Juliana [0000-0002-0127-579X], Daoud, Razan E. [0000-0001-7034-0770], Dattani, Nike [0000-0001-5667-3632], Decleva, Piero [0000-0002-7322-887X], de Graaf, Coen [0000-0001-8114-6658], Delcey, Mickaël G. [0000-0001-9883-3569], De Vico, Luca [0000-0002-2821-5711], Dobrautz, Werner [0000-0001-6479-1874], Dong, Sijia S. [0000-0001-8182-6522], Feng, Rulin [0000-0002-9812-3804], Ferré, Nicolas [0000-0002-5583-8834], Filatov Gulak, Michael [0000-0002-1541-739X], Gagliardi, Laura [0000-0001-5227-1396], Garavelli, Marco [0000-0002-0796-289X], González, Leticia [0000-0001-5112-794X], Guo, Meiyuan [0000-0003-2474-6264], Hennefarth, Matthew R. [0000-0002-6601-2253], Hermes, Matthew R. [0000-0001-7807-2950], Huix-Rotllant, Miquel [0000-0002-2131-7328], Jaiswal, Vishal Kumar [0000-0002-5090-7984], Kaliakin, Danil S. [0000-0002-9354-8248], King, Daniel S. [0000-0003-0208-5274], Larsson, Ernst D. [0000-0001-7655-2993], Lehtola, Susi [0000-0001-6296-8103], Lepetit, Marie-Bernadette [0000-0001-8730-4282], Lischka, Hans [0000-0002-5656-3975], Lundberg, Marcus [0000-0002-1312-1202], Mai, Sebastian [0000-0001-5327-8880], Marquetand, Philipp [0000-0002-8711-1533], Merritt, Isabella C. D. [0000-0002-7965-7798], Nenov, Artur [0000-0003-3071-5341], Nguyen, Vu Ha Anh [0000-0002-4177-0656], Nishimoto, Yoshio [0000-0001-5581-4712], Oakley, Meagan S. [0000-0001-5072-7572], Olivucci, Massimo [0000-0002-8247-209X], Oppel, Markus [0000-0001-6363-2310], Padula, Daniele [0000-0002-7171-7928], Pandharkar, Riddhish [0000-0003-4086-4308], Phung, Quan Manh [0000-0001-8205-5328], Plasser, Felix [0000-0003-0751-148X], Reiher, Markus [0000-0002-9508-1565], Rivalta, Ivan [0000-0002-1208-602X], Roca-Sanjuán, Daniel [0000-0001-6495-2770], Romig, Thies [0000-0002-9424-2398], Safari, Arta Anushirwan [0000-0003-4511-8902], Sánchez-Mansilla, Aitor [0000-0002-2601-190X], Sand, Andrew M. [0000-0002-7166-2066], Schapiro, Igor [0000-0001-8536-6869], Scott, Thais R. [0000-0002-5746-5517], Segarra-Martí, Javier [0000-0002-2076-3406], Segatta, Francesco [0000-0003-4150-6676], Sergentu, Dumitru-Claudiu [0000-0001-6570-5245], Shepard, Ron [0000-0002-0272-0824], Shu, Yinan [0000-0002-8371-0221], Sørensen, Lasse Kragh [0000-0002-1931-1867], Tenorio, Bruno Nunes Cabral [0000-0002-9702-998X], Truhlar, Donald G. [0000-0002-7742-7294], Ungur, Liviu [0000-0001-5015-4225], Vacher, Morgane [0000-0001-9418-6579], Veryazov, Valera [0000-0002-0172-7047], Li Manni, Giovanni, Fdez Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, L., Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov Gulak, Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J Patrick, Lindh, Roland, Fundación la Caixa, European Commission, Ministerio de Ciencia e Innovación (España), Department of Energy (US), Swiss National Science Foundation, Ministero dell'Istruzione, dell'Università e della Ricerca, Carl Trygger Foundation, Royal Society (UK), Independent Research Fund Denmark, German Research Foundation, Generalitat de Catalunya, Olle Engkvist Foundation, National Centre for Research and Development (Poland), National Science Foundation (US), Academy of Finland, Knut and Alice Wallenberg Foundation, Swedish Research Council, Université de Nantes, Japan Society for the Promotion of Science, Università degli Studi di Siena, Novo Nordisk Foundation, Argonne National Laboratory (US), National University of Singapore, Air Force Office of Scientific Research (US), Linköping University, Centre National de la Recherche Scientifique (France), Li Manni, Giovanni [0000-0002-3666-3880], Fdez Galván, Ignacio [0000-0002-0684-7689], #NODATA#, Aleotti, Flavia [0000-0002-7176-5305], Aquilante, Francesco [0000-0003-4422-3938], Autschbach, Jochen [0000-0001-9392-877X], Avagliano, Davide [0000-0001-5539-9731], Baiardi, Alberto [0000-0001-9112-8664], Bao, Jie J. [0000-0003-0197-3405], Battaglia, Stefano [0000-0002-5082-2681], Blanco-González, Alejandro [0000-0001-7379-2588], Bokarev, Sergey I. [0000-0003-0779-5013], Broer, Ria [0000-0002-5437-9509], Cacciari, Roberto [0000-0001-8290-4297], Calio, Paul B. [0000-0001-8385-2628], Carlson, Rebecca K. [0000-0002-1710-5816], Carvalho Couto, Rafael [0000-0003-4020-0923], Cerdán, L. [0000-0002-7174-2453], Chibotaru, Liviu F. [0000-0003-1556-0812], Chilton, Nicholas F. [0000-0002-8604-0171], Church, Jonathan Richard [0000-0001-5986-1305], Conti, Irene [0000-0001-7982-4480], Coriani, Sonia [0000-0002-4487-897X], Cuéllar-Zuquin, Juliana [0000-0002-0127-579X], Daoud, Razan E. [0000-0001-7034-0770], Dattani, Nike [0000-0001-5667-3632], Decleva, Piero [0000-0002-7322-887X], de Graaf, Coen [0000-0001-8114-6658], Delcey, Mickaël G. [0000-0001-9883-3569], De Vico, Luca [0000-0002-2821-5711], Dobrautz, Werner [0000-0001-6479-1874], Dong, Sijia S. [0000-0001-8182-6522], Feng, Rulin [0000-0002-9812-3804], Ferré, Nicolas [0000-0002-5583-8834], Filatov Gulak, Michael [0000-0002-1541-739X], Gagliardi, Laura [0000-0001-5227-1396], Garavelli, Marco [0000-0002-0796-289X], González, Leticia [0000-0001-5112-794X], Guo, Meiyuan [0000-0003-2474-6264], Hennefarth, Matthew R. [0000-0002-6601-2253], Hermes, Matthew R. [0000-0001-7807-2950], Huix-Rotllant, Miquel [0000-0002-2131-7328], Jaiswal, Vishal Kumar [0000-0002-5090-7984], Kaliakin, Danil S. [0000-0002-9354-8248], King, Daniel S. [0000-0003-0208-5274], Larsson, Ernst D. [0000-0001-7655-2993], Lehtola, Susi [0000-0001-6296-8103], Lepetit, Marie-Bernadette [0000-0001-8730-4282], Lischka, Hans [0000-0002-5656-3975], Lundberg, Marcus [0000-0002-1312-1202], Mai, Sebastian [0000-0001-5327-8880], Marquetand, Philipp [0000-0002-8711-1533], Merritt, Isabella C. D. [0000-0002-7965-7798], Nenov, Artur [0000-0003-3071-5341], Nguyen, Vu Ha Anh [0000-0002-4177-0656], Nishimoto, Yoshio [0000-0001-5581-4712], Oakley, Meagan S. [0000-0001-5072-7572], Olivucci, Massimo [0000-0002-8247-209X], Oppel, Markus [0000-0001-6363-2310], Padula, Daniele [0000-0002-7171-7928], Pandharkar, Riddhish [0000-0003-4086-4308], Phung, Quan Manh [0000-0001-8205-5328], Plasser, Felix [0000-0003-0751-148X], Reiher, Markus [0000-0002-9508-1565], Rivalta, Ivan [0000-0002-1208-602X], Roca-Sanjuán, Daniel [0000-0001-6495-2770], Romig, Thies [0000-0002-9424-2398], Safari, Arta Anushirwan [0000-0003-4511-8902], Sánchez-Mansilla, Aitor [0000-0002-2601-190X], Sand, Andrew M. [0000-0002-7166-2066], Schapiro, Igor [0000-0001-8536-6869], Scott, Thais R. [0000-0002-5746-5517], Segarra-Martí, Javier [0000-0002-2076-3406], Segatta, Francesco [0000-0003-4150-6676], Sergentu, Dumitru-Claudiu [0000-0001-6570-5245], Shepard, Ron [0000-0002-0272-0824], Shu, Yinan [0000-0002-8371-0221], Sørensen, Lasse Kragh [0000-0002-1931-1867], Tenorio, Bruno Nunes Cabral [0000-0002-9702-998X], Truhlar, Donald G. [0000-0002-7742-7294], Ungur, Liviu [0000-0001-5015-4225], Vacher, Morgane [0000-0001-9418-6579], Veryazov, Valera [0000-0002-0172-7047], Li Manni, Giovanni, Fdez Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, L., Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov Gulak, Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J Patrick, and Lindh, Roland

Abstract

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Published
2023

17. Compression of curium pyrrolidine-dithiocarbamate enhances covalency

Author

Sperling, Joseph M., Warzecha, Evan J., Celis-Barros, Cristian, Sergentu, Dumitru-Claudiu, Wang, Xiaoyu, Klamm, Bonnie E., and Windorff, Cory J.

Subjects
Carbamates -- Mechanical properties -- Chemical properties, Curium -- Mechanical properties -- Chemical properties, Chemical bonds -- Observations -- Mechanical properties -- Chemical properties, Amines -- Mechanical properties -- Chemical properties, Environmental issues, Science and technology, Zoology and wildlife conservation
Abstract

Curium is unique in the actinide series because its half-filled 5f .sup.7 shell has lower energy than other 5f .sup.n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell.sup.1-3. This is even more pronounced in gadolinium, curium's lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals.sup.4. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons.sup.5. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms.sup.5,6. Therefore, the question arises of whether the frontier metal orbitals in curium(iii)-ligand interactions can also be modified by applying pressure, and thus be induced to form metal-ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium-sulfur bonds in [Cm(pydtc).sub.4].sup.- (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc).sub.4].sup.- and of a Cm(iii) mellitate that possesses only curium-oxygen bonds. Compared with the changes observed in the [Cm(pydtc).sub.4].sup.- spectra, we observe smaller changes in the f-f transitions in the [Nd(pydtc).sub.4].sup.- absorption spectrum and in the f-f emission spectrum of the Cm(iii) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium-sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds. Enhanced covalency is achieved for a curium complex with curium-sulfur bonds by subjecting the compound to high pressures, indicating that pressure can be used to tune covalency in actinide compounds., Author(s): Joseph M. Sperling [sup.1] , Evan J. Warzecha [sup.1] , Cristian Celis-Barros [sup.1] , Dumitru-Claudiu Sergentu [sup.2] , Xiaoyu Wang [sup.2] , Bonnie E. Klamm [sup.1] , Cory J. [...]

Published
2020
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18. The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry

Author

Li Manni, Giovanni, primary, Fdez. Galván, Ignacio, additional, Alavi, Ali, additional, Aleotti, Flavia, additional, Aquilante, Francesco, additional, Autschbach, Jochen, additional, Avagliano, Davide, additional, Baiardi, Alberto, additional, Bao, Jie J., additional, Battaglia, Stefano, additional, Birnoschi, Letitia, additional, Blanco-González, Alejandro, additional, Bokarev, Sergey I., additional, Broer, Ria, additional, Cacciari, Roberto, additional, Calio, Paul B., additional, Carlson, Rebecca K., additional, Carvalho Couto, Rafael, additional, Cerdán, Luis, additional, Chibotaru, Liviu F., additional, Chilton, Nicholas F., additional, Church, Jonathan Richard, additional, Conti, Irene, additional, Coriani, Sonia, additional, Cuéllar-Zuquin, Juliana, additional, Daoud, Razan E., additional, Dattani, Nike, additional, Decleva, Piero, additional, de Graaf, Coen, additional, Delcey, Mickaël G., additional, De Vico, Luca, additional, Dobrautz, Werner, additional, Dong, Sijia S., additional, Feng, Rulin, additional, Ferré, Nicolas, additional, Filatov(Gulak), Michael, additional, Gagliardi, Laura, additional, Garavelli, Marco, additional, González, Leticia, additional, Guan, Yafu, additional, Guo, Meiyuan, additional, Hennefarth, Matthew R., additional, Hermes, Matthew R., additional, Hoyer, Chad E., additional, Huix-Rotllant, Miquel, additional, Jaiswal, Vishal Kumar, additional, Kaiser, Andy, additional, Kaliakin, Danil S., additional, Khamesian, Marjan, additional, King, Daniel S., additional, Kochetov, Vladislav, additional, Krośnicki, Marek, additional, Kumaar, Arpit Arun, additional, Larsson, Ernst D., additional, Lehtola, Susi, additional, Lepetit, Marie-Bernadette, additional, Lischka, Hans, additional, López Ríos, Pablo, additional, Lundberg, Marcus, additional, Ma, Dongxia, additional, Mai, Sebastian, additional, Marquetand, Philipp, additional, Merritt, Isabella C. D., additional, Montorsi, Francesco, additional, Mörchen, Maximilian, additional, Nenov, Artur, additional, Nguyen, Vu Ha Anh, additional, Nishimoto, Yoshio, additional, Oakley, Meagan S., additional, Olivucci, Massimo, additional, Oppel, Markus, additional, Padula, Daniele, additional, Pandharkar, Riddhish, additional, Phung, Quan Manh, additional, Plasser, Felix, additional, Raggi, Gerardo, additional, Rebolini, Elisa, additional, Reiher, Markus, additional, Rivalta, Ivan, additional, Roca-Sanjuán, Daniel, additional, Romig, Thies, additional, Safari, Arta Anushirwan, additional, Sánchez-Mansilla, Aitor, additional, Sand, Andrew M., additional, Schapiro, Igor, additional, Scott, Thais R., additional, Segarra-Martí, Javier, additional, Segatta, Francesco, additional, Sergentu, Dumitru-Claudiu, additional, Sharma, Prachi, additional, Shepard, Ron, additional, Shu, Yinan, additional, Staab, Jakob K., additional, Straatsma, Tjerk P., additional, Sørensen, Lasse Kragh, additional, Tenorio, Bruno Nunes Cabral, additional, Truhlar, Donald G., additional, Ungur, Liviu, additional, Vacher, Morgane, additional, Veryazov, Valera, additional, Voß, Torben Arne, additional, Weser, Oskar, additional, Wu, Dihua, additional, Yang, Xuchun, additional, Yarkony, David, additional, Zhou, Chen, additional, Zobel, J. Patrick, additional, and Lindh, Roland, additional

Published
2023
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19. The OpenMolcas Web : A Community-Driven Approach to Advancing Computational Chemistry

Author

Manni, Giovanni Li, Fernández Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-Gonzalez, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Couto, Rafael Carvalho, Cerdan, Luis, Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuellar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickael G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferre, Nicolas, Filatov (Gulak), Michael, Gagliardi, Laura, Garavelli, Marco, Gonzalez, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krosnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, Rios, Pablo Lopez, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Morchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuan, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sanchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Marti, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sorensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voss, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J. Patrick, Lindh, Roland, Manni, Giovanni Li, Fernández Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-Gonzalez, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Couto, Rafael Carvalho, Cerdan, Luis, Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuellar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickael G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferre, Nicolas, Filatov (Gulak), Michael, Gagliardi, Laura, Garavelli, Marco, Gonzalez, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krosnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie-Bernadette, Lischka, Hans, Rios, Pablo Lopez, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C. D., Montorsi, Francesco, Morchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuan, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sanchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Marti, Javier, Segatta, Francesco, Sergentu, Dumitru-Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sorensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voss, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J. Patrick, and Lindh, Roland

Abstract

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Published
2023
Full Text
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20. The OpenMolcas Web:A Community-Driven Approach to Advancing Computational Chemistry

Author

Li Manni, Giovanni, Fdez. Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, Luis, Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov(Gulak), Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C.D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J. Patrick, Lindh, Roland, Li Manni, Giovanni, Fdez. Galván, Ignacio, Alavi, Ali, Aleotti, Flavia, Aquilante, Francesco, Autschbach, Jochen, Avagliano, Davide, Baiardi, Alberto, Bao, Jie J., Battaglia, Stefano, Birnoschi, Letitia, Blanco-González, Alejandro, Bokarev, Sergey I., Broer, Ria, Cacciari, Roberto, Calio, Paul B., Carlson, Rebecca K., Carvalho Couto, Rafael, Cerdán, Luis, Chibotaru, Liviu F., Chilton, Nicholas F., Church, Jonathan Richard, Conti, Irene, Coriani, Sonia, Cuéllar-Zuquin, Juliana, Daoud, Razan E., Dattani, Nike, Decleva, Piero, de Graaf, Coen, Delcey, Mickaël G., De Vico, Luca, Dobrautz, Werner, Dong, Sijia S., Feng, Rulin, Ferré, Nicolas, Filatov(Gulak), Michael, Gagliardi, Laura, Garavelli, Marco, González, Leticia, Guan, Yafu, Guo, Meiyuan, Hennefarth, Matthew R., Hermes, Matthew R., Hoyer, Chad E., Huix-Rotllant, Miquel, Jaiswal, Vishal Kumar, Kaiser, Andy, Kaliakin, Danil S., Khamesian, Marjan, King, Daniel S., Kochetov, Vladislav, Krośnicki, Marek, Kumaar, Arpit Arun, Larsson, Ernst D., Lehtola, Susi, Lepetit, Marie Bernadette, Lischka, Hans, López Ríos, Pablo, Lundberg, Marcus, Ma, Dongxia, Mai, Sebastian, Marquetand, Philipp, Merritt, Isabella C.D., Montorsi, Francesco, Mörchen, Maximilian, Nenov, Artur, Nguyen, Vu Ha Anh, Nishimoto, Yoshio, Oakley, Meagan S., Olivucci, Massimo, Oppel, Markus, Padula, Daniele, Pandharkar, Riddhish, Phung, Quan Manh, Plasser, Felix, Raggi, Gerardo, Rebolini, Elisa, Reiher, Markus, Rivalta, Ivan, Roca-Sanjuán, Daniel, Romig, Thies, Safari, Arta Anushirwan, Sánchez-Mansilla, Aitor, Sand, Andrew M., Schapiro, Igor, Scott, Thais R., Segarra-Martí, Javier, Segatta, Francesco, Sergentu, Dumitru Claudiu, Sharma, Prachi, Shepard, Ron, Shu, Yinan, Staab, Jakob K., Straatsma, Tjerk P., Sørensen, Lasse Kragh, Tenorio, Bruno Nunes Cabral, Truhlar, Donald G., Ungur, Liviu, Vacher, Morgane, Veryazov, Valera, Voß, Torben Arne, Weser, Oskar, Wu, Dihua, Yang, Xuchun, Yarkony, David, Zhou, Chen, Zobel, J. Patrick, and Lindh, Roland

Abstract

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Published
2023

21. UN@C82: A U≡N Triple Bond Captured inside Fullerene Cages

Author

Chen, Ning, primary, Meng, Qingyu, additional, Abella, Laura, additional, Yao, Yang-Rong, additional, Sergentu, Dumitru-Claudiu, additional, Yang, Wei, additional, Liu, Xieye, additional, Zhuang, Jiaxin, additional, Echegoyen, Luis, additional, and Autschbach, Jochen, additional

Published
2022
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24. Correction: Enhanced 5f-δ bonding in [U(C7H7)2]-: C K-edge XAS, magnetism, and ab initio calculations

Author

Qiao, Yusen, Ganguly, Gaurab, Booth, Corwin H, Branson, Jacob A, Ditter, Alexander S, Lussier, Daniel J, Moreau, Liane M, Russo, Dominic R, Sergentu, Dumitru-Claudiu, Shuh, David K, Sun, Taoxiang, Autschbach, Jochen, and Minasian, Stefan G

Subjects
Chemical Sciences, Organic Chemistry
Abstract

Correction for 'Enhanced 5f-δ bonding in [U(C7H7)2]-: C K-edge XAS, magnetism, and ab initio calculations' by Yusen Qiao et al., Chem. Commun., 2021, 57, 9562-9565, DOI: 10.1039/D1CC03414F.

Published
2021

25. Equatorial Electronic Structure in the Uranyl Ion: Cs2UO2Cl4 and Cs2UO2Br4

Author

Sergentu, Dumitru-Claudiu, primary, Gendron, Frédéric, additional, Walter, Eric D., additional, Park, Sejun, additional, Capan, Cigdem, additional, Surbella, R. Gian, additional, Soderquist, Chuck Z., additional, Hall, Gabriel B., additional, Sinkov, Sergey I., additional, Autschbach, Jochen, additional, and Cho, Herman, additional

Published
2021
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27. A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages.

Author

Meng, Qingyu, Abella, Laura, Yao, Yang-Rong, Sergentu, Dumitru-Claudiu, Yang, Wei, Liu, Xinye, Zhuang, Jiaxin, Echegoyen, Luis, Autschbach, Jochen, and Chen, Ning

Subjects
DIATOMIC molecules, SOLID rare gases, CHARGE exchange, CHEMICAL bond lengths, OXIDATION states
Abstract

Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@Cs(6)-C82 and UN@C2(5)-C82, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@Cs(6)-C82 and UN@C2(5)-C82. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)2+@(C82)2− electronic structure with formal +5 oxidation state (f1) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species. Diatomic actinide molecules are ideal models for studying rare multiple-bond motifs. Here, the authors report host-guest structures of metastable charged U≡N diatoms confined in fullerene cages and stabilized by coordinative electron transfer. [ABSTRACT FROM AUTHOR]

Published
2022
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30. Correction: Enhanced 5f-δ bonding in [U(C7H7)2]−: C K-edge XAS, magnetism, and ab initio calculations

Author

Qiao, Yusen, primary, Ganguly, Gaurab, additional, Booth, Corwin H., additional, Branson, Jacob A., additional, Ditter, Alexander S., additional, Lussier, Daniel J., additional, Moreau, Liane M., additional, Russo, Dominic R., additional, Sergentu, Dumitru-Claudiu, additional, Shuh, David K., additional, Sun, Taoxiang, additional, Autschbach, Jochen, additional, and Minasian, Stefan G., additional

Published
2021
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31. Modern quantum chemistry with [Open]Molcas

Author

Aquilante, Francesco, Autschbach, Jochen, Baiardi, Alberto, Battaglia, Stefano, Borin, Veniamin A., Chibotaru, Liviu F., Conti, Irene, De Vico, Luca, Delcey, Mickael G, Fernández Galván, Ignacio, Ferre, Nicolas, Freitag, Leon, Garavelli, Marco, Gong, Xuejun, Knecht, Stefan, Larsson, Ernst D., Lindh, Roland, Lundberg, Marcus, Malmqvist, Per Ake, Nenov, Artur, Norell, Jesper, Odelius, Michael, Olivucci, Massimo, Pedersen, Thomas B., Pedraza-Gonzalez, Laura, Phung, Quan M., Pierloot, Kristine, Reiher, Markus, Schapiro, Igor, Segarra-Marti, Javier, Segatta, Francesco, Seijo, Luis, Sen, Saumik, Sergentu, Dumitru-Claudiu, Stein, Christopher J., Ungur, Liviu, Vacher, Morgane, Valentini, Alessio, Veryazov, Valera, Aquilante, Francesco, Autschbach, Jochen, Baiardi, Alberto, Battaglia, Stefano, Borin, Veniamin A., Chibotaru, Liviu F., Conti, Irene, De Vico, Luca, Delcey, Mickael G, Fernández Galván, Ignacio, Ferre, Nicolas, Freitag, Leon, Garavelli, Marco, Gong, Xuejun, Knecht, Stefan, Larsson, Ernst D., Lindh, Roland, Lundberg, Marcus, Malmqvist, Per Ake, Nenov, Artur, Norell, Jesper, Odelius, Michael, Olivucci, Massimo, Pedersen, Thomas B., Pedraza-Gonzalez, Laura, Phung, Quan M., Pierloot, Kristine, Reiher, Markus, Schapiro, Igor, Segarra-Marti, Javier, Segatta, Francesco, Seijo, Luis, Sen, Saumik, Sergentu, Dumitru-Claudiu, Stein, Christopher J., Ungur, Liviu, Vacher, Morgane, Valentini, Alessio, and Veryazov, Valera

Abstract

MOLCAS/OpenMolcas is an ab initio electronic structure program providing a large set of computational methods from Hartree-Fock and density functional theory to various implementations of multiconfigurational theory. This article provides a comprehensive overview of the main features of the code, specifically reviewing the use of the code in previously reported chemical applications as well as more recent applications including the calculation of magnetic properties from optimized density matrix renormalization group wave functions.

Published
2020
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32. Similar ligand–metal bonding for transition metals and actinides? 5f1 U(C7H7)2–versus 3dn metallocenes† †Electronic supplementary information (ESI) available: Additional support material comprising atomic spin populations, scans of potential energy surfaces and various CAS(PT2)-SR(SO) data. See DOI: 10.1039/c7sc05373h

Author

Sergentu, Dumitru-Claudiu, Gendron, Frédéric, and Autschbach, Jochen

Subjects
Chemistry
Abstract

A computational analysis of the electronic structure, bonding and magnetic properties in the 5f1 U(C7H7)2– complex vs. 3d metallocenes is performed. Notably, it is shown that the proton hyperfine coupling constant in U(C7H7)2– is the same in sign and magnitude to that of the 3d7 cobaltocene, but the two systems do not share a similar covalent metal–ligand bonding., U(C7H7)2– is a fascinating 5f1 complex whose metal–ligand bonding was assigned in the literature as being very similar to 3d7 cobaltocene, based on a crystal-field theoretical interpretation of the experimental magnetic resonance data. The present work provides an in-depth theoretical study of the electronic structure, bonding, and magnetic properties of the 5f1 U(C7H7)2–vs. 3d metallocenes with V, Co, and Ni, performed with relativistic wavefunction and density functional methods. The ligand to metal donation bonding in U(C7H7)2– is strong and in fact similar to that in vanadocene, in the sense that the highest occupied arene orbitals donate electron density into empty metal orbitals of the same symmetry with respect to the rotational axis (3dπ for V, 5fδ for U), but selectively with α spin (↑). For Co and Ni, the dative bonding from the ligands is β spin (↓) selective into partially filled 3dπ orbitals. In all systems, this spin delocalization triggers spin polarization in the arene σ bonding framework, causing proton spin densities opposite to those of the carbons. As a consequence, the proton spin densities and hyperfine coupling constants are negative for the Co and Ni complex, but positive for vanadocene. The of U(C7H7)2– is negative and similar to that of cobaltocene, but only because of the strong spin–orbit coupling in the actinocene, which causes to be opposite to the sign of the proton spin density. The study contributes to a better understanding of actinide 5f vs. transition metal 3d covalency, and highlights potential pitfalls when interpreting experimental magnetic resonance data in terms of covalent bonding for actinide complexes.

Published
2018

34. Correction to “Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages”

Author

Zhuang, Jiaxin, primary, Abella, Laura, additional, Sergentu, Dumitru-Claudiu, additional, Yao, Yang-Rong, additional, Jin, Meihe, additional, Yang, Wei, additional, Zhang, Xingxing, additional, Li, Xiaomeng, additional, Zhang, Duo, additional, Zhao, Yiming, additional, Li, Xiaohong, additional, Wang, Shuao, additional, Echegoyen, Luis, additional, Autschbach, Jochen, additional, and Chen, Ning, additional

Published
2020
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37. Modern quantum chemistry with [Open]Molcas

Author

Aquilante, Francesco, primary, Autschbach, Jochen, additional, Baiardi, Alberto, additional, Battaglia, Stefano, additional, Borin, Veniamin A., additional, Chibotaru, Liviu F., additional, Conti, Irene, additional, De Vico, Luca, additional, Delcey, Mickaël, additional, Fdez. Galván, Ignacio, additional, Ferré, Nicolas, additional, Freitag, Leon, additional, Garavelli, Marco, additional, Gong, Xuejun, additional, Knecht, Stefan, additional, Larsson, Ernst D., additional, Lindh, Roland, additional, Lundberg, Marcus, additional, Malmqvist, Per Åke, additional, Nenov, Artur, additional, Norell, Jesper, additional, Odelius, Michael, additional, Olivucci, Massimo, additional, Pedersen, Thomas B., additional, Pedraza-González, Laura, additional, Phung, Quan M., additional, Pierloot, Kristine, additional, Reiher, Markus, additional, Schapiro, Igor, additional, Segarra-Martí, Javier, additional, Segatta, Francesco, additional, Seijo, Luis, additional, Sen, Saumik, additional, Sergentu, Dumitru-Claudiu, additional, Stein, Christopher J., additional, Ungur, Liviu, additional, Vacher, Morgane, additional, Valentini, Alessio, additional, and Veryazov, Valera, additional

Published
2020
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41. Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages

Author

Zhuang, Jiaxin, primary, Abella, Laura, additional, Sergentu, Dumitru-Claudiu, additional, Yao, Yang-Rong, additional, Jin, Meihe, additional, Yang, Wei, additional, Zhang, Xingxing, additional, Li, Xiaomeng, additional, Zhang, Duo, additional, Zhao, Yiming, additional, Li, Xiaohong, additional, Wang, Shuao, additional, Echegoyen, Luis, additional, Autschbach, Jochen, additional, and Chen, Ning, additional

Published
2019
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42. Calculs relativistes pour l'identification de nouvelles espèces chimiques aux ultra-traces

Author

Sergentu, Dumitru-Claudiu, Guo, Ning, Teze, David, Champion, Julie, Montavon, Gilles, Galland, Nicolas, Maurice, Rémi, Laboratoire SUBATECH Nantes (SUBATECH), Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Nantes (UN)-Mines Nantes (Mines Nantes), 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), Laboratoire de physique subatomique et des technologies associées (SUBATECH), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

National audience

Published
2018

43. Enhanced 5f-δ bonding in [U(C7H7)2]−: C K-edge XAS, magnetism, and ab initio calculations.

Author

Qiao, Yusen, Ganguly, Gaurab, Booth, Corwin H., Branson, Jacob A., Ditter, Alexander S., Lussier, Daniel J., Moreau, Liane M., Russo, Dominic R., Sergentu, Dumitru-Claudiu, Shuh, David K., Sun, Taoxiang, Autschbach, Jochen, and Minasian, Stefan G.

Subjects
AB-initio calculations, X-ray absorption, STRUCTURAL analysis (Engineering), X-ray spectroscopy, ELECTRONIC structure
Abstract

5f covalency in [U(C7H7)2]− was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results revealed U 5f orbital participation in δ-bonding in both the ground- and core-excited states; additional 5f φ-mixing is observed in the core-excited states. Comparisons with U(C8H8)2 show greater δ-covalency for [U(C7H7)2]−. [ABSTRACT FROM AUTHOR]

Published
2021
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44. Electronic structures and geometries of the XF3 (X = Cl, Br, I, At) fluorides.

Author

Sergentu, Dumitru-Claudiu, Amaouch, Mohamed, Pilmé, Julien, Galland, Nicolas, and Maurice, Rémi

Subjects
*ELECTRONIC structure, *FLUORIDES, *POTENTIAL energy surfaces, *WAVE functions, *CARBON isotopes, *MOLECULAR structure, *PHYSICS experiments
Abstract

The potential energy surfaces of the group 17 XF3 (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C2v structures are computed for ClF3, BrF3, and IF3, while we predict that an average D3h structure would be experimentally observed for AtF3. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D3h geometry and the C2v one, along the XF3 series, and in the X = At case, spin-orbit coupling also slightly reduces this energy difference. AtF3 is a borderline system where the D3h structure becomes a minimum, i.e., the pseudo- Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C2v minima, although both types of effects interfere. [ABSTRACT FROM AUTHOR]

Published
2015
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45. Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L3‐edge Puzzle.

Author

Sergentu, Dumitru‐Claudiu, Booth, Corwin H., and Autschbach, Jochen

Subjects
*CERIUM, *EXCITED states, *OXIDATION states, *SPECTROMETRY, *PUZZLES, *X-ray absorption near edge structure
Abstract

The Ce L3 edge XAS spectra of CeO2 and cerocene [Ce(C8H8)2] were calculated with relativistic ab‐initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades‐long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core‐excited states (ESs). CeO2 and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f‐shell occupations and the value derived from XAS measurements using peak areas (nf). The identity of the two‐peaked Ce L3 edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f1 vs. 4f0 sub‐configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f2 sub‐configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining nf from Ce L3‐edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of nf by calculations, is stressed. [ABSTRACT FROM AUTHOR]

Published
2021
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46. Probing chemical bonds at the relativistic and multiconfigurational level: Effective bond orders and topological analyses

Author

Gomez Pech, Cecilia, Haase, Pi A. B., Sergentu, Dumitru-Claudiu, Galland, Nicolas, Borschevsky, Anastasia, Pilmé, Julien, Maurice, Rémi, Laboratoire de physique subatomique et des technologies associées (SUBATECH), 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 National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), University of Groningen [Groningen], Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire SUBATECH Nantes (SUBATECH), and Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Nantes (UN)-Mines Nantes (Mines Nantes)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2018

49. Hunting invisible astatine: An excuse to study the role of spin-orbit coupling on chemical bonding?

Author

Gomez Pech, Cecilia, Sergentu, Dumitru-Claudiu, Galland, Nicolas, Maurice, Rémi, Laboratoire de physique subatomique et des technologies associées (SUBATECH), 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 National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), and Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017

50. Géométries, structures électroniques et propriétés physico-chimiques d’espèces de l’astate : une application de la mécanique quantique relativiste

Author

Sergentu, Dumitru-Claudiu, Laboratoire de physique subatomique et des technologies associées (SUBATECH), 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 National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Nantes, and Nicolas Galland

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, spin-orbit configuration interaction, astate, effets relativistes, astatine, théorie de la fonctionnelle de la densité, interaction de configuration avec couplage spin-orbite, density functional theory, relativistic effects
Abstract

Trials to destroy cancer cells with currently synthesized 211At-based radiotherapeutic agents are not yet fully satisfactorily since they resume to in vivo deastatination. Since this issue is related to the limited knowledge of the basic chemistry of At and its species, fundamental researches combining ultra-trace experiments and computational studies have been initiated. In this thesis, a computational study of several At species is performed, by means of relativistic density functional theory and wave-function-based calculations. First, the quantum mechanical approaches that can safely be used to make adequate predictions are established. Using these approaches, we attempt to rationalize the electronic structures, geometries, and physico-chemical properties of various systems of theoretical and/or experimental interest, in particular the AtF3 and AtO+ ones. By the end, we firmly identify a new At species by combining outcomes of experiments and calculations. This new species not only completes the Pourbaix diagram of At in aqueous and non-complexing media, but also gives clues of identifying experimental conditions to make best reactive the At– precursor, which is currently involved in the synthesis of promising radiotherapeutic agents.; Les tentatives menées pour détruire des cellules cancéreuses avec les agents radiothérapeutiques à base de 211At qui ont été synthétisés jusqu’à présent ne sont pas encore pleinement satisfaisantes car elles sont entachées par une deastatination in vivo. Étant donné que ce problème est lié aux connaissances actuelles qui sont limitées concernant la chimie de base de l’astate et de ses espèces, des recherches fondamentales combinant des expériences à l’échelle des ultra-traces et des études théoriques ont été lancées. Dans cette thèse, une étude théorique de plusieurs espèces de l’astate est réalisée au moyen de méthodes relativistes basées sur la théorie de la fonctionnelle de la densité ou des méthodes à basées sur la fonction d’onde. Tout d'abord, les méthodes qui peuvent être utilisées pour faire des prédictions pertinentes sont établies. A l’aide de ces approches, nous rationaliserons les structures électroniques, géométries et propriétés physico-chimiques des différents systèmes d'intérêt théorique ou expérimental, en particulier les espèces AtF3 et AtO+. Finalement, nous identifierons formellement une nouvelle espèce de l’astate à l’aide de résultats expérimentaux et de calculs, ce qui non seulement complète le diagramme de Pourbaix de l’astate en milieu aqueux non complexant, mais aussi donne des informations cruciales pour identifier des conditions expérimentales pour rendre le plus « réactif » possible le précurseur At−, qui est de nos jours impliqué dans la synthèse d’agents radiothérapeutiques innovants.

Published
2016

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