162 results on '"Enrico Bodo"'
Search Results
2. Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
- Author
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Adriano Pierini, Sergio Brutti, and Enrico Bodo
- Subjects
Materials of engineering and construction. Mechanics of materials ,TA401-492 ,Computer software ,QA76.75-76.765 - Abstract
Abstract The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprotic media catalyzed by group 1A cations. Our analysis is based on ab initio multireference computational methods and unveils the competition between the expected reactive path leading to peroxide and an unexpected reaction channel that involves the reduction of the alkaline ion. Both channels lead to the release of triplet and singlet O2. The existence of this reduction channel not only facilitates singlet oxygen release but leads to a reactive neutral solvated species that can onset parasitic chemistries due to their well-known reducing properties. Overall, we show that the application of moderate overpotentials makes both these channels accessible in aprotic batteries.
- Published
- 2021
- Full Text
- View/download PDF
3. About the Formation of NH2OH+ from Gas Phase Reactions under Astrochemical Conditions
- Author
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Gabriele Dilena, Simone Pistillo, and Enrico Bodo
- Subjects
interstellar medium ,gas-phase chemistry ,hydroxylamine ,Organic chemistry ,QD241-441 - Abstract
We present here an analysis of several possible reactive pathways toward the formation of hydroxylamine under astrochemical conditions. The analysis is based on ab initio quantum chemistry calculations. Twenty-one bimolecular ion–molecule reactions have been studied and their thermodynamics presented. Only one of these reactions is a viable direct route to hydroxylamine. We conclude that the contribution of gas-phase chemistry to hydroxylamine formation is probably negligible when compared to its formation via surface grain chemistry. However, we have found several plausible gas-phase reactions whose outcome is the hydroxylamine cation.
- Published
- 2023
- Full Text
- View/download PDF
4. A Computational Analysis of the Reaction of SO2 with Amino Acid Anions: Implications for Its Chemisorption in Biobased Ionic Liquids
- Author
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Vanessa Piacentini, Andrea Le Donne, Stefano Russo, and Enrico Bodo
- Subjects
SO2 capture ,amino acids ,ionic liquids ,Organic chemistry ,QD241-441 - Abstract
We report a series of calculations to elucidate one possible mechanism of SO2 chemisorption in amino acid-based ionic liquids. Such systems have been successfully exploited as CO2 absorbents and, since SO2 is also a by-product of fossil fuels’ combustion, their ability in capturing SO2 has been assessed by recent experiments. This work is exclusively focused on evaluating the efficiency of the chemical trapping of SO2 by analyzing its reaction with the amino group of the amino acid. We have found that, overall, SO2 is less reactive than CO2, and that the specific amino acid side chain (either acid or basic) does not play a relevant role. We noticed that bimolecular absorption processes are quite unlikely to take place, a notable difference with CO2. The barriers along the reaction paths are found to be non-negligible, around 7–11 kcal/mol, and the thermodynamic of the reaction appears, from our models, unfavorable.
- Published
- 2022
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5. Hydrogen Bonding as a Clustering Agent in Protic Ionic Liquids: Like-Charge vs Opposite-Charge Dimer Formation
- Author
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Andrea Le Donne, Henry Adenusi, Francesco Porcelli, and Enrico Bodo
- Subjects
Chemistry ,QD1-999 - Published
- 2018
- Full Text
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6. Theoretical Insights into the Structure of the Aminotris(Methylenephosphonic Acid) (ATMP) Anion: A Possible Partner for Conducting Ionic Media
- Author
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Henry Adenusi, Gregory Chass, and Enrico Bodo
- Subjects
ionic liquids ,semiempirical methods ,DFTB ,proton transfer ,Mathematics ,QA1-939 - Abstract
We present a computational characterisation of Aminotris(methylenephosphonic acid) (ATMP) and its potential use as an anionic partner for conductive ionic liquids (ILs). We argue that for an IL to be a good candidate for a conducting medium, two conditions must be fulfilled: (i) the charge must be transported by light carriers; and (ii) the system must maintain a high degree of ionisation. The result trends presented herein show that there are molecular ion combinations that do comply with these two criteria, regardless of the specific system used. ATMP is a symmetric molecule with a total of six protons. In the bulk phase, breaking the symmetry of the fully protonated state and creating singly and doubly charged anions induces proton transfer mechanisms. To demonstrate this, we used molecular dynamics (MD) simulations employing a variable topology approach based on the reasonably reliable semiempirical density functional tight binding (DFTB) evaluation of the atomic forces. We show that, by choosing common and economical starting compounds, we can devise a viable prototype for a highly conductive medium where charge transfer is achieved by proton motion.
- Published
- 2020
- Full Text
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7. Structural Features of Triethylammonium Acetate through Molecular Dynamics
- Author
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Enrico Bodo
- Subjects
molecular dynamics ,semi-empirical methods ,ionic liquids ,Organic chemistry ,QD241-441 - Abstract
I have explored the structural features and the dynamics of triethylammonium acetate by means of semi-empirical (density functional tight binding, DFTB) molecular dynamics. I find that the results from the present simulations agree with recent experimental determinations with only few minor differences in the structural interpretation. A mixture of triethylamine and acetic acid does not form an ionic liquid, but gives rise to a very complex system where ionization is only a partial process affecting only few molecules (1 over 4 experimentally). I have also found that the few ionic couples are stable and remain mainly embedded inside the AcOH neutral moiety.
- Published
- 2020
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8. Aluminium catalysed oligomerisation in cement-forming silicate systems
- Author
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Mohammed S. Salha, Rickey Y. Yada, David H. Farrar, Gregory A. Chass, Kun V. Tian, and Enrico Bodo
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General Physics and Astronomy ,Physical and Theoretical Chemistry - Abstract
Alumino-silicates form the backbone of structural materials including cements and the concrete they form. However, the nanoscale aspects of the oligomerisation mechanisms elongating the (alumino-)silicate chains is not fully clarified; the role of aluminium in particular. Herein, we explore and contrast the growth of silicate and alumino-silicate oligomers by both neutral and anionic mechanisms, with focus on the influence of Al on oligomer structure and stability. Further, the spontaneity of chain lengthening in the absence and presence of Al of differing coordination (Al-IV, V, VI) was characterised. Result trends showed Al-IV facilitating oligomerisation in neutral conditions, with respect to Si only systems, effectively promoting longer chain formation and stabilisation. The anionic pathway similarly showed Al reducing the overall energetic barriers to oligomerisation. In both conditions, Al's coordinative and structural flexibility, at O-Al-O hinge points in particular, was responsible for the lowering of the energetic expense for oligomerisation. The results and implications resolved herein are informative for chain formation and stability for bulk material properties of alumino-silicate materials such as cements, where the aluminosilicate systems are dominated by short chains of 2-5 units in length.
- Published
- 2023
9. A polarisable force field for bio-compatible ionic liquids based on amino acids anions
- Author
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Stefano Russo and Enrico Bodo
- Subjects
General Chemical Engineering ,Modeling and Simulation ,General Materials Science ,General Chemistry ,Condensed Matter Physics ,Information Systems - Published
- 2022
10. Final Products of One-Electron Oxidation of Cyclic Dipeptides Containing Methionine Investigated by IRMPD Spectroscopy: Does the Free Radical Choose the Final Compound?
- Author
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Yining Jiang, Suvasthika Indrajith, Ariel Francis Perez Mellor, Thomas Bürgi, Marc Lecouvey, Carine Clavaguéra, Enrico Bodo, Chantal Houée-Levin, Estelle Loire, Giel Berden, Jos Oomens, Debora Scuderi, Institut de Chimie Physique (ICP), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Stockholm University, Université de Genève = University of Geneva (UNIGE), Chimie, Structures et Propriétés de Biomatériaux et d'Agents Thérapeutiques (CSPBAT), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Sorbonne Paris Nord, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Radboud University [Nijmegen], van ‘t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam (UvA), and Molecular Spectroscopy (HIMS, FNWI)
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FELIX Molecular Structure and Dynamics ,IRMPD spectroscopy ,Spectrum Analysis ,-radiolysis ,One-electron oxidation ,cyclic peptides ,Electrons ,Dipeptides ,Hydrogen Peroxide ,Sulfenic Acids ,Surfaces, Coatings and Films ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,Methionine ,One-electron oxidation -radiolysis IRMPD spectroscopy tandem mass spectrometry cyclic peptides ,tandem mass spectrometry ,Materials Chemistry ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Physical and Theoretical Chemistry ,Sulfur - Abstract
Reactive oxygen species (ROS) such as hydrogen peroxide (H2O2) and the hydroxyl radical (•OH) have specific functions in biological processes, while their uncontrolled production and reactivity are known to be determining factors in pathophysiology. Methionine (Met) residues act as endogenous antioxidants, when they are oxidized into methionine sulfoxide (MetSO), thus depleting ROS and protecting the protein. We employed tandem mass spectrometry combined with IR multiple photon dissociation spectroscopy to study the oxidation induced by OH radicals produced by γradiolysis on model cyclic dipeptides c(LMetLMet), c(LMetDMet), and c(GlyMet). Our aim was to characterize the geometries of the oxidized peptides in the gas phase and to understand the relationship between the structure of the 2-center 3-electron (2c-3e) free radical formed in the first step of the oxidation process and the final compound. Density functional theory calculations were performed to characterize the lowest energy structures of the final product of oxidation and to interpret the IR spectra. Collision-induced dissociation tandem mass spectrometry (CID-MS2) experiments of oxidized c(LMetLMet)H+ and c(LMetDMet)H+ led to the loss of one or two oxidized sulfenic acid molecules, indicating that the addition of one or two oxygen atoms occurs on the sulfur atom of both methionine side chains and no sulfone formation was observed. The CID-MS2 fragmentation mass spectrum of oxidized c(GlyMet)H+ showed only the loss of one oxidized sulfenic acid molecule. Thus, the final products of oxidation are the same regardless of the structure of the precursor sulfur-centered free radical.
- Published
- 2022
11. Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
- Author
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Enrico Bodo, Adriano Pierini, and Sergio Brutti
- Subjects
ab-initio calculations ,Singlet oxygen ,Superoxide ,Ab initio ,chemistry.chemical_element ,Disproportionation ,Photochemistry ,Oxygen ,Peroxide ,electrochemistry ,Li-O2 batteries ,Computer Science Applications ,Catalysis ,chemistry.chemical_compound ,QA76.75-76.765 ,chemistry ,Mechanics of Materials ,Modeling and Simulation ,TA401-492 ,General Materials Science ,Singlet state ,Computer software ,Materials of engineering and construction. Mechanics of materials - Abstract
The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprotic media catalyzed by group 1A cations. Our analysis is based on ab initio multireference computational methods and unveils the competition between the expected reactive path leading to peroxide and an unexpected reaction channel that involves the reduction of the alkaline ion. Both channels lead to the release of triplet and singlet O2. The existence of this reduction channel not only facilitates singlet oxygen release but leads to a reactive neutral solvated species that can onset parasitic chemistries due to their well-known reducing properties. Overall, we show that the application of moderate overpotentials makes both these channels accessible in aprotic batteries.
- Published
- 2021
12. Anharmonic Aspects in Vibrational Circular Dichroism Spectra from 900 to 9000 cm
- Author
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Marco, Fusè, Giovanna, Longhi, Giuseppe, Mazzeo, Stefano, Stranges, Francesca, Leonelli, Giorgia, Aquila, Enrico, Bodo, Bruno, Brunetti, Carlo, Bicchi, Cecilia, Cagliero, Julien, Bloino, and Sergio, Abbate
- Abstract
Vibrational circular dichroism (VCD) spectra and the corresponding IR spectra of the chiral isomers of methyloxirane and of methylthiirane have been reinvestigated, both experimentally and theoretically, with particular attention to accounting for anharmonic corrections, as calculated by the GVPT2 approach. De novo recorded VCD spectra in the near IR (NIR) range regarding CH-stretching overtone transitions, together with the corresponding NIR absorption spectra, were also considered and accounted for, both with the GVPT2 and with the local mode approaches. Comparison of the two methods has permitted us to better describe the nature of active "anharmonic" modes in the two molecules and the role of mechanical and electrical anharmonicity in determining the intensities of VCD and IR/NIR data. Finally, two nonstandard IR/NIR regions have been investigated: the first one about ≈2000 cm
- Published
- 2022
13. Advanced Raman Spectroscopy Detection of Oxidative Damage in Nucleic Acid Bases: Probing Chemical Changes and Intermolecular Interactions in Guanosine at Ultralow Concentration
- Author
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Simonetta Palleschi, Filomena Mazzei, Enrico Bodo, Paolo Postorino, Chunchun Li, Margherita Bignami, Marina Ceccarini, Claudia Fasolato, Steven E. J. Bell, Francesca Ripanti, and Flavia Mazzarda
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Guanine ,Guanosine ,FOS: Physical sciences ,oxidative damage ,medicine.disease_cause ,Spectrum Analysis, Raman ,Article ,Analytical Chemistry ,chemistry.chemical_compound ,symbols.namesake ,Physics - Chemical Physics ,Nucleic Acids ,medicine ,Nucleotide ,Physics - Biological Physics ,chemistry.chemical_classification ,Chemical Physics (physics.chem-ph) ,Chemistry ,Nucleotides ,Raman spectroscopy ,DNA ,Oxidative Stress ,Biological Physics (physics.bio-ph) ,Nucleic acid ,Biophysics ,symbols ,Oxidative stress ,Raman scattering - Abstract
DNA/RNA synthesis precursors are especially vulnerable to damage induced by reactive oxygen species occurring following oxidative stress. Guanosine triphosphates are the prevalent oxidized nucleosites, which can be misincorporated during replication, leading to mutations and cell death. Here, we present a novel method based on micro-Raman spectroscopy, combined with ab initio calculations, for the identification, detection, and quantification of low concentrations of oxidized nucleotides. We also show that the Raman signature in the terahertz spectral range (< 100 cm$^{-1}$) contains information on the intermolecular assembly of guanine in tetrads, which allows to further boost the oxidative damage detection limit. Eventually, we provide evidence that similar analyses can be carried out on samples in very small volumes at very low concentrations by exploiting the high sensitivity of Surface Enhanced Raman Scattering combined with properly designed superhydrophobic substrates. These results pave the way for employing such advanced spectroscopic methods for quantitatively sensing the oxidative damage of nucleotides in the cell., 11 pages, 7 figures
- Published
- 2021
14. Cholinium amino acid-based ionic liquids
- Author
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Andrea Le Donne and Enrico Bodo
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chemistry.chemical_classification ,Cholinium ,Low toxicity ,Chemistry ,Biophysics ,Biocompatible ionic liquids ,amino acids ,biocompatible ionic liquids ,cholinium ,Ionic liquids ,02 engineering and technology ,Review ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Special class ,01 natural sciences ,0104 chemical sciences ,Amino acid ,chemistry.chemical_compound ,Structural Biology ,Ionic liquid ,Organic chemistry ,Amino acids ,0210 nano-technology ,Molecular Biology - Abstract
Boosted by the simplicity of their synthesis and low toxicity, cholinium and amino acid-based ionic liquids have attracted the attention of researchers in many different fields ranging from computational chemistry to electrochemistry and medicine. Among the uncountable IL variations, these substances occupy a space on their own due to their exceptional biocompatibility that stems from being entirely made by metabolic molecular components. These substances have undergone a rather intensive research activity because of the possibility of using them as greener replacements for traditional ionic liquids. We present here a short review in the attempt to provide a compendium of the state-of-the-art scientific research about this special class of ionic liquids based on the combination of amino acid anions and cholinium cations.
- Published
- 2021
15. Modelling biocompatible ionic liquids based on organic acids and amino acids: challenges for computational models and future perspectives
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Enrico Bodo
- Subjects
chemistry.chemical_classification ,Computational model ,Chemistry ,Organic Chemistry ,Ionic Liquids ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Biocompatible material ,01 natural sciences ,Biochemistry ,0104 chemical sciences ,Amino acid ,chemistry.chemical_compound ,Ionic liquid ,ioni liquids ,Biochemical engineering ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
In this short review I shall highlight the basic principle and the difficulties that arise in attempting the computational modeling of seemingly simple systems which hide an unexpected complexity. Biocompatible ionic liquids which are based on the coupling of organic or amino acid anions with metabolic cations such as cholinium are the target of this review. These substances have been the subject of intense research activities in the last few years and have attracted the attention of computational chemists. I shall show that the computational description of these substances is far from trivial and requires the use of sophisticated techniques in order to account for a surprisingly rich chemistry that is due to several phenomena such as polarization, charge transfer, proton transfer equilibria and tautomerization reactions.
- Published
- 2021
16. CO2 Capture in Ionic Liquids Based on Amino Acid Anions With Protic Side Chains: a Computational Assessment of Kinetically Efficient Reaction Mechanisms
- Author
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Stefano Onofri, Enrico Bodo, Andrea Le Donne, and Henry Adenusi
- Subjects
Reaction mechanism ,Glycine ,Ionic Liquids ,010402 general chemistry ,01 natural sciences ,chemistry.chemical_compound ,Carbamic acid ,Computational chemistry ,CO2 storage ,Side chain ,green solvents ,Homocysteine ,chemistry.chemical_classification ,Aspartic Acid ,Full Paper ,010405 organic chemistry ,protic side chains ,Water ,General Chemistry ,Full Papers ,Carbon Dioxide ,computational chemistry ,0104 chemical sciences ,Amino acid ,Kinetics ,chemistry ,Models, Chemical ,Yield (chemistry) ,Ionic liquid ,Thermodynamics ,Carbamates ,Absorption (chemistry) ,Derivative (chemistry) - Abstract
Absorption and capture of CO2 directly from sources represents one of the major tools to reduce its emission in the troposphere. One of the possibilities is to incorporate CO2 inside a liquid exploiting its propensity to react with amino groups to yield carbamic acid or carbamates. A particular class of ionic liquids, based on amino acids, appear to represent a possible efficient medium for CO2 capture because, at difference with current industrial setups, they have the appeal of a biocompatible and environmentally benign solution. We have investigated, by means of highly accurate computations, the feasibility of the reaction that incorporates CO2 in an amino acid anion with a protic side chain and ultimately transforms it into a carbamate derivative. Through an extensive exploration of the possible reaction mechanisms, we have found that different prototypes of amino acid anions present barrierless reaction mechanisms toward CO2 absorption., Fully biocompatible ionic liquids based on aminoacid anions are possible candidates for CO2 absorption and storage. Accurate, ab‐initio computations provide indications about the mechanisms of the reaction of CO2 with the aminoacid anions and a guide for the overall efficiency of the CO2 absorption process.
- Published
- 2020
17. Superoxide Anion Disproportionation Induced by Li + and H + : Pathways to 1 O 2 Release in Li−O 2 Batteries
- Author
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Enrico Bodo, Adriano Pierini, and Sergio Brutti
- Subjects
Superoxide ,Disproportionation ,02 engineering and technology ,Electronic structure ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Photochemistry ,Kinetic energy ,01 natural sciences ,Peroxide ,Atomic and Molecular Physics, and Optics ,0104 chemical sciences ,Catalysis ,Ion ,chemistry.chemical_compound ,chemistry ,Impurity ,Physical and Theoretical Chemistry ,0210 nano-technology - Abstract
We explore the disproportionation reaction of superoxide anions in the presence of H+ and Li+ cations with high quality multiconfigurational ab-initio methods. This reaction is of paramount importance in Li-O2 battery chemistry as it represents the source of a major degrading impurity, singlet molecular oxygen. For the first time, the thermodynamic and kinetic data of the reaction are drawn from an accurate theoretical model where the electronic structure of the reactant and products is treated at the necessary level of theory. Overall, the H+ catalyzed O2- +O2- disproportionation follows a very efficient thermodynamic and kinetic reaction path leading to neutral 3 O2 , 1 O2 and peroxide anions. On the contrary, we have found that the Li+ catalysis promotes only the release of 3 O2 whereas the 1 O2 formation is energetically unfeasible at room temperature.
- Published
- 2020
18. Anharmonic aspects in vibrational circular dichroism spectra from 900 to 9000 cm-1 for methyloxirane and methylthiirane
- Author
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Marco Fusè, Giovanna Longhi, Giuseppe Mazzeo, Stefano Stranges, Francesca Leonelli, Giorgia Aquila, Enrico Bodo, Bruno Brunetti, Carlo Bicchi, Cecilia Cagliero, Julien Bloino, and Sergio Abbate
- Subjects
anharmonic ,Physical and Theoretical Chemistry ,methylthiirane ,vibrational circular dichroism - Published
- 2022
19. Unusually chemoselective photocyclization of 2-(hydroxyimino)aldehydes to cyclobutanol oximes. synthetic, stereochemical, and mechanistic aspects
- Author
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Antonio Di Sabato, Francesca D’Acunzo, Dario Filippini, Fabrizio Vetica, Antonio Brasiello, Davide Corinti, Enrico Bodo, Cinzia Michenzi, Edoardo Panzetta, and Patrizia Gentili
- Subjects
2-(hydroxyimino)aldehydes ,Aldehydes ,photochemistry ,norrish-yang reaction ,Organic Chemistry ,Oximes ,photoisomerization ,cyclobutanol oximes ,Cyclobutanes ,Ethers - Abstract
Photocyclization of carbonyl compounds (known as the Norrish-Yang reaction) to yield cyclobutanols is, in general, accompanied by fragmentation reactions. The latter are predominant in the case of aldehydes so that secondary cyclobutanols are not considered accessible via the straightforward Norrish-Yang reaction. A noteworthy exception has been reported in our laboratory, where cyclobutanols bearing a secondary alcohol function were observed upon UV light irradiation of 2-(hydroxyimino)aldehydes (HIAs). This reaction is here investigated in detail by combining synthesis, spectroscopic data, molecular dynamics, and DFT calculations. The synthetic methodology is generally applicable to a series of HIAs, affording the corresponding cyclobutanol oximes (CBOs) chemoselectively (i.e., without sizable fragmentation side-reactions), diastereoselectively (up to99:1), and in good to excellent yields (up to 95%). CBO oxime ether derivatives can be purified and diastereomers isolated by standard column chromatography. The mechanistic and stereochemical picture of this photocyclization reaction, as well as of the postcyclization
- Published
- 2022
20. Excited state dynamics of Zn-salophen complexes
- Author
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Patrick O’Keeffe, Daniele Catone, Stefano Turchini, Alessandra Paladini, Antonella Dalla Cort, Enrico Bodo, and Susanna Piccirillo
- Subjects
Salophen ,Time dependent density functional theory ,Zinc ,Ultrafast transient absorption ,parasitic diseases ,Adenosine diphosphate ,Fluorescence emission ,Physical and Theoretical Chemistry ,Settore CHIM/03 ,Ligands ,Salicylates - Abstract
Zn–salophen complexes are a promising class of fluorescent chemosensors for nucleotides and nucleic acids. We have investigated, by means of steady state UV–Vis, ultrafast transient absorption, fluorescence emission and time dependent density functional theory (TD-DFT) the behavior of the excited states of a salicylidene tetradentate Schiff base (Sal), its Zn(II) coordination compound (Zn–Sal) and the effect of the interaction between Zn–Sal and adenosine diphosphate (ADP). TD-DFT shows that the deactivation of the excited state of Sal occurs through torsional motion, due to its rotatable bonds and twistable angles. Complexation with Zn(II) causes rigidity so that the geometry changes in the excited states with respect to the ground state structure are minimal. By addition of ADP to a freshly prepared Zn–Sal ethanol solution, a longer relaxation constant, in comparison to Zn–Sal, was measured, indicative of the interaction between Zn–Sal and ADP. After a few days, the Zn–Sal–ADP solution displayed the same static and dynamic behavior of a solution containing only the Sal ligand, demonstrating that the coordination of the ADP anion to Zn(II)leads to the demetallation of the Sal ligand. Fluorescence measurements also revealed an enhanced fluorescence at 375 nm following the addition of ADP to the solution, caused by the presence of 2,3-diamino naphthalene that is formed by demetallation and partial decomposition of the Sal ligand. The efficient fluorescence of this species at 375 nm could be selectively detected and used as a probe for the detection of ADP in solution. Graphical abstract
- Published
- 2022
21. ASPIN: An all spin scattering code for atom-molecule rovibrationally inelastic cross sections.
- Author
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David López-Durán, Enrico Bodo, and Franco A. Gianturco
- Published
- 2008
- Full Text
- View/download PDF
22. Study of the Electronic Structure of Alkali Peroxides and Their Role in the Chemistry of Metal-Oxygen Batteries
- Author
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Enrico Bodo, Adriano Pierini, and Sergio Brutti
- Subjects
Chemistry ,Superoxide ,Ab initio ,Trimer ,Electronic structure ,Electrochemistry ,Alkali metal ,Peroxide ,Article ,Metal ,chemistry.chemical_compound ,visual_art ,visual_art.visual_art_medium ,Physical chemistry ,Li-O2 batteries ,Physical and Theoretical Chemistry - Abstract
We use a multiconfigurational and correlated ab initio method to investigate the fundamental electronic properties of the peroxide MO2- (M = Li and Na) trimer to provide new insights into the rather complex chemistry of aprotic metal-O2 batteries. These electrochemical systems are largely based on the electronic properties of superoxide and peroxide of alkali metals. The two compounds differ by stoichiometry: the superoxide is characterized by a M+O2- formula, while the peroxide is characterized by [M+]2O22-. We show here that both the peroxide and superoxide states necessarily coexist in the MO2- trimer and that they correspond to their different electronic states. The energetic prevalence of either one or the other and the range of their coexistence over a subset of the MO2- nuclear configurations is calculated and described via a high-level multiconfigurational approach.
- Published
- 2021
23. Structural Features of Cholinium Based Protic Ionic Liquids through Molecular Dynamics
- Author
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Henry Adenusi, Andrea Le Donne, Francesco Porcelli, and Enrico Bodo
- Subjects
chemistry.chemical_classification ,Quantitative Biology::Biomolecules ,010304 chemical physics ,Proton ,Hydrogen bond ,Charge (physics) ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Ion ,Amino acid ,chemistry.chemical_compound ,Molecular dynamics ,chemistry ,Chemical physics ,0103 physical sciences ,Ionic liquid ,Physics::Atomic and Molecular Clusters ,Materials Chemistry ,Charge carrier ,hydrogen bonds ,ionic liquids ,molecular dynamics ,Physics::Chemical Physics ,Physical and Theoretical Chemistry - Abstract
An analysis of the complex proton transfer processes in certain protic ionic liquids, based on amino acid anions, has been carried out through ab initio molecular dynamics in the view of finding naturally conductive and pure mediums. The systems analyzed here might serve as chemical prototypes for pure and dry ionic liquids where mobile protons can act as fast charge carriers. We have exploited the natural tendency of these liquids to form a complex network of hydrogen bonds. The presence of such a network allows the naturally repulsive interaction between like charge ions to be weakened to the point that a proton migration process inside the anionic component of the fluid becomes possible. We have also seen that the extent of these proton migrations is sizable for carboxylic based amino acid anions, while it is very limited for sulfur containing ones.
- Published
- 2019
24. Ultra-Fast-VUV Photoemission Study of UV Excited 2-Nitrophenol
- Author
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Carlo Spezzani, Fabio Frassetto, Susanna Piccirillo, Antti Kivimäki, Marco Pezzella, Alessandra Ciavardini, Simonetta Fornarini, Enrico Bodo, Paolo Miotti, Carlo Callegari, Cesare Grazioli, Carla Puglia, Barbara Ressel, Monica de Simone, Giovanni De Ninno, Luca Poletto, and Marcello Coreno
- Subjects
Photodissociation ,photochemistry ,photoelectron spectroscopy ,Proton ,Ab initio ,010402 general chemistry ,01 natural sciences ,Molecular physics ,X-ray photoelectron spectroscopy ,Fragmentation (mass spectrometry) ,nitrophenol ,0103 physical sciences ,High harmonic generation ,Physical and Theoretical Chemistry ,femtosecond ,Excited state dynamics ,Settore CHIM/03 - Chimica Generale e Inorganica ,010304 chemical physics ,Chemistry ,0104 chemical sciences ,Intersystem crossing ,Photodissociation, Excited state dynamics, femtosecond, photoelectron spectroscopy ,Excited state ,ultrafast emission ,Ultrashort pulse - Abstract
The initial deactivation pathways of gaseous 2-nitrophenol excited at 268 nm were investigated by time-resolved photoelectron spectroscopy (TRPES) with femtosecond-VUV light, produced by a monochromatized high harmonic generation source. TRPES allowed us to obtain new, valuable experimental information about the ultrafast excited-state dynamics of 2-nitrophenol in the gas phase. In accord with recent ab initio on-The-fly nonadiabatic molecular dynamic simulations, our results validate the occurrence of an ultrafast intersystem crossing leading to an intermediate state that decays on a subpicosecond time scale with a branched mechanisms. Two decay pathways are experimentally observed. One probably involves proton transfer, leading to the most stable triplet aci-form of 2-nitrophenol; the second pathway may involve OH rotation. We propose that following intersystem crossing, an ultrafast fragmentation channel leading to OH or HONO loss could also be operative.
- Published
- 2019
25. Contributors
- Author
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B.L. Bhargava, Enrico Bodo, M. Natália D.S. Cordeiro, Chengna Dai, Leon Engelbrecht, Elisabete S.C. Ferreira, Benny K. George, Shohei Kakinuma, Volodymyr A. Koverga, Andrea Le Donne, Zhigang Lei, Alessandro Mariani, Alina Adriana Minea, Francesca Mocci, Stefano Passerini, Carlos M. Pereira, Hideaki Shirota, Sajini T, Eapen Thomas, Minu Elizabeth Thomas, Jince Thomas, K.P. Vijayalakshmi, Iuliia V. Voroshylova, and Gangqiang Yu
- Published
- 2021
26. Assessing the Structure of Protic Ionic Liquids Based on Triethylammonium and Organic Acid Anions
- Author
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Alessandro Mariani, Matteo Bonomo, and Enrico Bodo
- Subjects
chemistry.chemical_classification ,Technology ,010304 chemical physics ,Chemistry ,Hydrogen bond ,Binding energy ,Ionic Liquids ,Protonation ,010402 general chemistry ,Electrostatics ,01 natural sciences ,Article ,0104 chemical sciences ,Surfaces, Coatings and Films ,chemistry.chemical_compound ,Computational chemistry ,0103 physical sciences ,Ionic liquid ,Materials Chemistry ,Physical and Theoretical Chemistry ,Trifluoromethanesulfonate ,Triethylamine ,ddc:600 ,Organic acid - Abstract
We present a computational analysis of the short-range structure of three protic ionic liquids based on strong organic acids: trifluoracetate, methanesulfonate, and triflate of triethylammonium. Accurate ab initio computations carried out on the gas-phase dimers show that the protonation of triethylamine is spontaneous. We have identified the anion-cation binding motif that is due to the presence of a strong hydrogen bond and to electrostatic interactions. The strength of the hydrogen bond and the magnitude of the binding energy decrease in the order trifluoroacetate ≳ methanesulfonate > triflate. The corresponding simulations of the bulk phases, obtained using a semiempirical evaluation of the interatomic forces, reveal that on short timescales, the state of the three liquids remains highly ionized and that the gas-phase cation-/anion-binding motif is preserved while no other peculiar structural features seem to emerge.
- Published
- 2021
27. Hydrogen bonding in biocompatible ionic liquids: an ab-initio characterization of dimeric interactions
- Author
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Andrea Le Donne, Henry Adenusi, Francesco Porcelli, and Enrico Bodo
- Subjects
biocompatible ionic liquids ,coupled cluster ,hydrogen bonds ,ionic liquids ,Chemistry ,Hydrogen bond ,Ab initio ,Condensed Matter Physics ,Biocompatible material ,Electronic, Optical and Magnetic Materials ,Characterization (materials science) ,chemistry.chemical_compound ,Ionic liquid ,Electrochemistry ,Materials Chemistry ,Physical chemistry ,Electrical and Electronic Engineering - Published
- 2021
28. CO2 Capture in Biocompatible Amino Acid Ionic Liquids: Exploring the Reaction Mechanisms for Bimolecular Absorption Processes
- Author
-
Stefano Onofri and Enrico Bodo
- Subjects
Anions ,Reaction mechanism ,010304 chemical physics ,Chemistry ,Ionic Liquids ,Context (language use) ,Carbon Dioxide ,010402 general chemistry ,01 natural sciences ,CO2 capture ,Article ,0104 chemical sciences ,Surfaces, Coatings and Films ,Ion ,chemistry.chemical_compound ,Chemisorption ,Computational chemistry ,Yield (chemistry) ,0103 physical sciences ,Ionic liquid ,Materials Chemistry ,Molecule ,Physical and Theoretical Chemistry ,Absorption (chemistry) ,Amino Acids - Abstract
CO2 capture at the production site represents one of the accessible ways to reduce its emission in the atmosphere. In this context, CO2 chemisorption is particularly advantageous and is often based on exploiting a liquid containing amino groups that can trap CO2 due to their propensity to react with it to yield carbamic derivatives. A well-known class of ionic liquids based on amino acid anions might represent an ideal medium for CO2 capture because, at difference with present implementations, they are known to be fully biocompatible. One of the problems is however the relatively low molar ratio of CO2 absorption. Increasing this ratio turns out to be possible by choosing appropriate anions. We present here a set of accurate computations to elucidate the possible reaction paths that allow the anion to absorb two CO2 molecules, thus effectively doubling the overall intake. An extensive exploration of some reaction mechanisms suggests that some of them might be quite efficient even under mild conditions.
- Published
- 2021
29. Welcome to Liquids: An Open Access Journal
- Author
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Enrico Bodo
- Subjects
Political science ,Library science ,Open access journal - Abstract
We are thrilled to launch “Liquids” as a peer-reviewed open access journal [...]
- Published
- 2021
30. Reactions in non-aqueous alkali and alkaline-earth metal-oxygen batteries: a thermodynamic study
- Author
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Enrico Bodo, Adriano Pierini, and Sergio Brutti
- Subjects
Singlet oxygen ,Inorganic chemistry ,Ab initio ,General Physics and Astronomy ,chemistry.chemical_element ,Disproportionation ,Electrochemistry ,Alkali metal ,Peroxide ,Redox ,Oxygen ,chemistry.chemical_compound ,chemistry ,Li-O2 batteries ,Physical and Theoretical Chemistry - Abstract
Multivalent aprotic metal–oxygen batteries are a novel concept in the applied electrochemistry field. These systems are variants of the so-called Li–air batteries and up to present are in their research infancy. The superoxide disproportionation reaction is a crucial step for the operation of any metal–oxygen redox system using aprotic solvents: in the best scenario, disproportionation leads to peroxide formation while in the worse one it releases singlet molecular oxygen. In this work we address the fundamental thermodynamics of such reaction for alkali (Li, Na and K) and alkaline earth (Be, Mg and Ca) metal–O2 systems using multiconfigurational ab initio methods. Our aim is to draw a comprehensive description of the disproportionation reaction from superoxides to peroxides and to provide the thermodynamic likelihood of the pathways to singlet oxygen release.
- Published
- 2021
31. Disclosing the hierarchical structure of ionic liquid mixtures by multiscale computational methods
- Author
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Leon de Villiers Engelbrecht, Francesca Mocci, Alessandro Mariani, Stefano Passerini, Andrea Le Donne, and Enrico Bodo
- Subjects
chemistry.chemical_compound ,Molecular dynamics ,chemistry ,Computer science ,Scattering ,Structure (category theory) ,Binary number ,Point (geometry) ,Density functional theory ,Ethylammonium nitrate ,Statistical physics ,Characterization (materials science) - Abstract
This chapter deals with the structural analysis of ionic liquid-containing mixtures through multiscale computational methods. The chapter is divided into two sections, dealing with a basic introduction to the topic, and a more in-depth presentation of four different computational methods typically used to simulate the structural and dynamical properties of complex liquid systems. Initially, the concept of the structure of a liquid is discussed, providing definitions and some examples. Subsequently, the main features of the experimental technique based on X-ray scattering are presented, which allow accessing structural information of amorphous systems. A short introduction of the laws governing the scattering phenomenon, and how scattered photons can provide information about the structure of a system is also presented. A significant part of this chapter is devoted to introducing four of the most used state-of-the-art computational methods, namely density functional theory “static” optimization, semiempirical molecular dynamics, classical molecular dynamics, and coarse-grained molecular dynamics. The starting point is the quantastic treatment of the system, in which only minimal approximations are used. The reader is then guided toward successive approximations enabling to explore different system sizes and timescales. The intricate system ethylammonium nitrate:acetonitrile 1:9 binary mixture is taken as a case study to show what the four obtained models can return in terms of characterization. The final picture describes how the various methods are fundamentally complementary to each other, meaning that there is nothing as a “best” method.
- Published
- 2021
32. Superoxide Anion Disproportionation Induced by Li
- Author
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Adriano, Pierini, Sergio, Brutti, and Enrico, Bodo
- Abstract
We explore the disproportionation reaction of superoxide anions in the presence of H
- Published
- 2020
33. Ab Initio Molecular Dynamics Study of Phospho-Amino Acid-Based Ionic Liquids: Formation of Zwitterionic Anions in the Presence of Acidic Side Chains
- Author
-
Francesco Porcelli, Enrico Bodo, Henry Adenusi, and Andrea Le Donne
- Subjects
chemistry.chemical_classification ,Quenching (fluorescence) ,010304 chemical physics ,Chemical structure ,Ab initio ,Ionic bonding ,010402 general chemistry ,01 natural sciences ,Article ,0104 chemical sciences ,Surfaces, Coatings and Films ,Amino acid ,chemistry.chemical_compound ,Molecular dynamics ,chemistry ,Computational chemistry ,0103 physical sciences ,Ionic liquid ,Materials Chemistry ,Side chain ,Physical and Theoretical Chemistry - Abstract
We present a computational analysis of the complex proton-transfer processes in two protic ionic liquids based on phosphorylated amino acid anions. The structure and the short time dynamics have been analyzed via ab initio and semi-empirical molecular dynamics. Given the presence of mobile protons on the side chain, such ionic liquids may represent a viable prototype of highly conductive ionic mediums. The results of our simulations are not entirely satisfactory in this respect. Our results indicate that conduction in these liquids may be limited due to a quick quenching of the proton-transfer processes. In particular, we have found that, while proton migration does occur on very short timescales, the amino groups act as proton scavengers preventing an efficient proton migration. Despite their limits as conductive mediums, we show that these ionic liquids possess an unconventional microscopic structure, where the anionic component is made by amino acid anions that the aforementioned proton transfer has transformed into zwitterionic isomers. This unusual chemical structure is relevant because of the recent use of amino acid-based ionic liquids, such as CO2 absorbent.
- Published
- 2020
34. Assessing the propensity toward ionization in nanosized clusters of protic ionic liquids by Ab-initio methods
- Author
-
Enrico Bodo, Stefano Russo, and Andrea Le Donne
- Subjects
chemistry.chemical_classification ,Base (chemistry) ,Proton ,Ab initio ,General Physics and Astronomy ,Ionic bonding ,Ionic liquids ,chemistry.chemical_compound ,chemistry ,Chemical physics ,Ionization ,Ionic liquid ,Cluster (physics) ,Molecule ,Physical and Theoretical Chemistry - Abstract
Nanosized clusters of protic ionic liquids are investigated using ab-initio DFT methods to understand their propensity to remain ionic. Protic ionic liquids are based on acid/base pairs and are ionic because of proton transfer from the acid to the base. Two prototypical ionic liquids based on triethylamine and two acids of different strengths are used here to trace the tendency toward proton transfer when the system size is gradually increased from an isolated pair of molecules to cluster of several pairs. We have found that the compounds based on the weak acid shows the existence of a well-defined minimal size that represents the threshold for the onset of ionization phenomena.
- Published
- 2022
35. Hydrogen Bonding as a Clustering Agent in Protic Ionic Liquids: Like-Charge vs Opposite-Charge Dimer Formation
- Author
-
Enrico Bodo, Henry Adenusi, Francesco Porcelli, and Andrea Le Donne
- Subjects
Materials science ,General Chemical Engineering ,Dimer ,microstructure ,Ab initio ,molecular structure ,02 engineering and technology ,amino acids ,distribution function ,enthalpy ,phase ,solvation ,viscosity ,010402 general chemistry ,01 natural sciences ,Article ,lcsh:Chemistry ,Molecular dynamics ,Viscosity ,Homologous series ,chemistry.chemical_compound ,Side chain ,Physics::Atomic and Molecular Clusters ,Physics::Chemical Physics ,Hydrogen bond ,General Chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,chemistry ,lcsh:QD1-999 ,Chemical physics ,Ionic liquid ,0210 nano-technology - Abstract
Open in a separate window The local structure of a series of homologous protic ionic liquids (PILs) is investigated using ab initio computations and ab initio-based molecular dynamics. The purpose of this work is to show that in PILs the network of hydrogen bonds may promote like-charge clustering between anionic species. We correlate the theoretical evidence of this possibility with viscosity experimental data. The homologous series of liquids is obtained by coupling choline with amino acid anions and varying the side chain. We find that the frictional properties of the liquids are clearly connected to the ability of the side chain to establish additional hydrogen bonds (other than the trivial cation–anion interaction). We also show that the large variation of bulk properties along the series of compounds can be explained by assuming that one of the sources of friction in the bulk liquid is the like-charge interaction between anions.
- Published
- 2018
36. Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations
- Author
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Simonetta Fornarini, Maria Elisa Crestoni, Enrico Bodo, Barbara Chiavarino, and Debora Scuderi
- Subjects
chemistry.chemical_classification ,010401 analytical chemistry ,Organic Chemistry ,Infrared spectroscopy ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Catalysis ,Dissociation (chemistry) ,0104 chemical sciences ,Amino acid ,chemistry.chemical_compound ,Crystallography ,Deprotonation ,chemistry ,Organic chemistry ,Carboxylate ,Infrared multiphoton dissociation ,Conformational isomerism ,Cysteine - Abstract
The redox activity of cysteine sulfur allows numerous post-translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas-phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSOx ]- (x=1, 2, 3, representing the number of S-bound oxygen atoms), which are key intermediates in the redox-switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur-containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO- in [cysSO]- migrates to the carboxylate in [cysSO3 ]- , whereas it turns out to be shared in [cysSO2 ]- . Evidence is gathered that a mixture of close-lying low-energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature.
- Published
- 2016
37. On the formation of propylene oxide from propylene in space: gas-phase reactions
- Author
-
Giulia Bovolenta, Riccardo Spezia, Chloe Simha, Enrico Bodo, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Laboratoire de chimie théorique (LCT), and Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
astrochemistry ,chirality ,quantum chemistry ,Materials science ,Astrochemistry ,010304 chemical physics ,Electron capture ,Kinetics ,010402 general chemistry ,Space (mathematics) ,7. Clean energy ,01 natural sciences ,Quantum chemistry ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,13. Climate action ,Ionization ,0103 physical sciences ,Physical chemistry ,Propylene oxide ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Physical and Theoretical Chemistry ,Chirality (chemistry) - Abstract
In the present article, we have investigated the possibility of forming propylene oxide (PO) from propylene (PE) by bi-molecular reactions. Propylene oxide is the first chiral molecule observed in the interstellar medium, and studying the thermodynamics and kinetics of formation can suggest possible synthetic routes. We have focused our attention on gas-phase reactions, and the presence of an environment is discussed in particular for the possibility of forming it by association reactions. In particular, we have considered radical and ion–molecule reactions. Results show that the main gas-phase route to PO formation is represented by ion–molecule reactions which turn out to be compatible with astrophysical conditions, notably: $$\hbox {PE} + \hbox {O}^{+}$$ and $$\hbox {PE} + \hbox {HO}_2^{+}$$ . Their final product is not PO, but its ionized variant $$\hbox {PO}^{+}$$ that can be neutralized by electron capture. The only thermodynamically and kinetically allowed reaction which can directly lead to neutral PO is a collision of PE with a singlet-excited $$\hbox {OH}^{+}$$ but two competing reactions (leading to $$\hbox {PE}^{+}$$ and $$\hbox {PO}^{+}$$ ) are thermodynamically favored and thus more plausible in space.
- Published
- 2019
38. Vibrational signatures of curcumin's chelation in copper(II) complexes: An appraisal by IRMPD spectroscopy
- Author
-
Simonetta Fornarini, Philippe Maître, Maria Elisa Crestoni, Debora Scuderi, Davide Corinti, Enrico Bodo, Alessandro Maccelli, Barbara Chiavarino, Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Dipartimento di Studi di Chimica e Tecnologia delle Sostanze Biologicamente Attive, Laboratoire de Chimie Physique D'Orsay (LCPO), and Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
010304 chemical physics ,Chemistry ,Electrospray ionization ,General Physics and Astronomy ,Infrared spectroscopy ,Protonation ,010402 general chemistry ,01 natural sciences ,Dissociation (chemistry) ,0104 chemical sciences ,Metal ,Crystallography ,Deprotonation ,[CHIM.ANAL]Chemical Sciences/Analytical chemistry ,visual_art ,0103 physical sciences ,visual_art.visual_art_medium ,[CHIM]Chemical Sciences ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Infrared multiphoton dissociation ,physics and astronomy (all) ,physical and theoretical chemistry ,Physical and Theoretical Chemistry ,Spectroscopy ,ComputingMilieux_MISCELLANEOUS - Abstract
Curcumin (Cur) is a natural polyphenol with a wide spectrum of biological activities and appealing therapeutic potential. Herein, it has been delivered by electrospray ionization as gaseous protonated species, [Cur + H]+, and as a Cu(ii) complex, [Cu(Cur - H)]+, a promising antioxidant and radical scavenger. The gas phase structures were assayed by infrared multiple photon dissociation (IRMPD) spectroscopy in both the fingerprint (800-2000 cm-1) and hydrogen stretching (3100-3750 cm-1) ranges. Comparison between the experimental features and linear IR spectra of the lowest energy structures computed at the B3LYP/6-311+G(d,p) level reveals that bare [Cu(Cur - H)]+ exists in a fully planar and symmetric arrangement, where the metal interacts with the two oxygens of the syn-enolate functionality of deprotonated Cur and both OCH3 groups are engaged in H-bonding with the ortho OH. The effect of protonation on the energetic and geometric determinants of Cur has been explored as well, revealing that bare [Cur + H]+ may exist as a mixture of two close-lying isomers associated with the most stable binding motifs. The additional proton is bound to either the diketo or the keto-enol configuration of Cur, in a bent or nearly planar arrangement, respectively.
- Published
- 2019
39. An experimental and theoretical investigation of XPS and NEXAFS of 5-halouracils
- Author
-
Lorenzo Avaldi, Enrico Bodo, Mattea Carmen Castrovilli, Paola Bolognesi, Giuseppe Mattioli, and Antonella Cartoni
- Subjects
X Ray-absorption ,infrared-laser spectroscopy ,photoelectron spectroscopy ,helium nanodroplets ,shell excitation ,small molecules ,carbon dioxide ,amino acids ,5-halouracil ,Materials science ,010304 chemical physics ,synchrotron radiation ,General Physics and Astronomy ,010402 general chemistry ,01 natural sciences ,DFT ,Spectral line ,XANES ,0104 chemical sciences ,Electronegativity ,X-ray photoelectron spectroscopy ,Ionization ,0103 physical sciences ,Halogen ,Physical chemistry ,Molecule ,XPS/NEXAFS ,Physical and Theoretical Chemistry ,Absorption (chemistry) - Abstract
The C, N and O 1s excitation and ionization processes of 5X-uracil (X = F, Cl, Br, and I) were investigated using near edge X-ray absorption fine structure (NEXAFS) and X-ray photoemission (XPS) spectroscopies. This study aims at the fine assessment of the effects of the functionalization of uracil molecules by halogen atoms having different electronegativity and bound to the same molecular site. Two DFT-based approaches, which rely on different paradigms, have been used to simulate the experimental spectra and to assign the corresponding features. The analysis of the screening of the core holes of the different atoms via electronic charge density plots has turned out to be a useful tool to illustrate the competition between the partially aromatic and partially conjugate properties of this class of molecules.
- Published
- 2018
40. Isomerization patterns and proton transfer in ionic liquids constituents as probed by ab-initio computation
- Author
-
Enrico Bodo and Andrea Le Donne
- Subjects
Proton ,010405 organic chemistry ,ionic liquids ,molecular dynamics ,Analytical chemistry ,010402 general chemistry ,Condensed Matter Physics ,Electrochemistry ,01 natural sciences ,Tautomer ,Atomic and Molecular Physics, and Optics ,0104 chemical sciences ,Electronic, Optical and Magnetic Materials ,Ion ,chemistry.chemical_compound ,Deprotonation ,chemistry ,Computational chemistry ,Ionic liquid ,Materials Chemistry ,Side chain ,Physical and Theoretical Chemistry ,Isomerization ,Spectroscopy - Abstract
We have recently shown that some protic ionic liquids (PILs) are characterized by an unexpected complex dynamic of proton transfer (M. Campetella et al., Phys. Chem. Chem. Phys. 19, 11,869, (2017)). These liquids are based on a combination of cholinium cations and amino acid (AA) deprotonated anions. The side chain proton migration, can take place both within the same anion and between different anions. The intra-molecular proton transfer leads to a tautomerization of the AA anion that gives rise to the appearance of an anionic zwitterionic form. The inter-molecular proton transfer is chemically more interesting since it might, at least in principle, point to a way to achieve a dry, fast conduction in materials that are otherwise very viscous and typically poor conductors. We examine here, by means of ab-initio computations, the basic mechanism of proton transfer in a variety of AA anions to find promising candidates as new materials for electrochemistry applications.
- Published
- 2018
41. Hydrogen Bonding Features in Cholinium-Based Protic Ionic Liquids from Molecular Dynamics Simulations
- Author
-
Maddalena Daniele, Stefano Lupi, Lorenzo Gontrani, Enrico Bodo, Andrea Le Donne, Francesca Leonelli, Marco Campetella, and Campetella Marco , Le Donne Andrea,Daniele Maddalena , Gontrani Lorenzo , Lupi Stefano , Bodo Enrico ,Leonelli Francesca
- Subjects
Materials science ,Ionic liquids | liquids | protic ionic ,Infrared spectroscopy ,electrolytes ,02 engineering and technology ,010402 general chemistry ,Branching (polymer chemistry) ,01 natural sciences ,Ion ,chemistry.chemical_compound ,Molecular dynamics ,Settore CHIM/02 ,Materials Chemistry ,Physics::Atomic and Molecular Clusters ,clusters ,phase ,Physical and Theoretical Chemistry ,Physics::Chemical Physics ,Alkyl ,chemistry.chemical_classification ,complexes ,Hydrogen bond ,Charge density ,x-ray diffraction ,bronsted acid-base ,aminoacid ,spectroscopic evidence ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Surfaces, Coatings and Films ,chemistry ,Chemical physics ,Ionic liquid ,choline aminoacis, ionic liquids,X-Ray diffraction, Ab initio molecular dynamics ,0210 nano-technology - Abstract
We explore the structure of a series of protic Ionic Liquids based on the choline cation and amino acid anions. In the series, the length and the branching of the amino acid alkyl chain varies. Ab initio molecular dynamics, X-ray diffraction measurements, and infrared spectra have been used to provide a reliable picture of the short-range structure and of the short-time dynamic process that characterize the fluids. We have put special emphasis on the peculiar and complicated network of hydrogen bonds that stem from the amphoteric nature of the anion moiety. The use of ab initio molecular dynamics allows us to calculate the “exact” charge density of the system and hence to obtain fairly accurate infrared spectra that, in turn, have been used to assign the experimental ones.
- Published
- 2018
42. Structural and energetic properties of La3+ in water/DMSO mixtures
- Author
-
Enrico Bodo, Riccardo Spezia, Maria Montagna, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Saclay (COmUE), ANR-10-JCJC-0807,ACLASOLV,Solvatation d'actinides et lanthanides(2010), and Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome]
- Subjects
Solvation shell ,Solvent molecules ,Polarizable force field ,Thermodynamics ,Solvation ,Molecular dynamics ,010402 general chemistry ,01 natural sciences ,Force field (chemistry) ,Analytical Chemistry ,Inorganic Chemistry ,Computational chemistry ,Polarizability ,0103 physical sciences ,medicine ,Molecule ,Shells (structures) ,Dehydration ,Dehydration process ,Energetic properties ,Spectroscopy ,Extraction of waters ,010304 chemical physics ,Chemistry ,analytical chemistry ,spectroscopy ,organic chemistry ,inorganic chemistry ,Organic Chemistry ,Equimolar mixtures ,Molecules ,medicine.disease ,0104 chemical sciences ,Solvent ,Mixtures ,Constrained dynamics ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] - Abstract
International audience; By using molecular dynamics based on a custom polarizable force field, we have studied the solvation of La3+ in an equimolar mixture of dimethylsulfoxide (DMSO) with water. An extended structural analysis has been performed to provide a complete picture of the physical properties at the basis of the interaction of La3+ with both solvents. Through our simulations we found that, very likely, the first solvation shell in the mixture is not unlike the one found in pure water or pure DMSO and contains 9 solvent molecules. We have also found that the solvation is preferentially due to DMSO molecules with the water initially present in first shell quickly leaving to the bulk. The dehydration process of the first shell has been analyzed by both plain MD simulations and a constrained dynamics approach; the free energy profiles for the extraction of water from first shell have also been computed.
- Published
- 2017
43. Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell
- Author
-
Enrico Bodo
- Subjects
Lanthanide ,Ionic radius ,Ligand ,Metal ions in aqueous solution ,Coordination number ,Surfaces, Coatings and Films ,Ion ,chemistry.chemical_compound ,solvents ,anions ,molecules ,ions ,chemistry ,Ionic liquid ,Materials Chemistry ,Organic chemistry ,Physical chemistry ,Ethylammonium nitrate ,Physical and Theoretical Chemistry - Abstract
By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).
- Published
- 2015
44. Solvation Properties of the Actinide Ion Th(IV) in DMSO and DMSO:Water Mixtures through Polarizable Molecular Dynamics
- Author
-
Riccardo Spezia, Maria Montagna, Enrico Bodo, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Saclay (COmUE), and Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome]
- Subjects
aqueous-solution ,actinides ,hydration structure ,010405 organic chemistry ,Chemistry ,Dimethyl sulfoxide ,Solvation ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Ion ,Inorganic Chemistry ,Solvent ,Molecular dynamics ,chemistry.chemical_compound ,Solvation shell ,Polarizability ,Computational chemistry ,Molecule ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,Physical and Theoretical Chemistry - Abstract
International audience; We have studied the solvation of Th4+ in water, in dimethyl sulfoxide (DMSO), and in their equimolar mixture by using molecular dynamics based on an Amoeba-derived polarizable force field. We have performed an extended structural analysis in order to provide a complete picture of the chemical–physical features of the interaction of Th4+ with the two solvents in their pure and mixed states. Through our simulations we found that, very likely, the first solvation shell in DMSO is not unlike the one found in pure water and contains 9 solvent molecules. The residence time of first shell of DMSO molecules is however much longer than the residence time of water. For the 1:1 mixture we present computational evidence that both water and DMSO participate in the solvation of Th4+ with a slight preference for the latter.
- Published
- 2017
45. Experimental and Computational Investigation of Salophen-Zn Gas Phase Complexes with Cations: A Source of Possible Interference in Anionic Recognition
- Author
-
Debora Scuderi, Enrico Bodo, Simonetta Fornarini, Alessandra Ciavardini, Susanna Piccirillo, and Antonella Dalla Cort
- Subjects
binding ,Stereochemistry ,photon dissociation spectroscopy ,free-electron laser ,infrared-spectroscopy ,irmpd spectroscopy ,metal-complexes ,zinc ,derivatives ,motifs ,model ,Protonation ,010402 general chemistry ,01 natural sciences ,Ion ,chemistry.chemical_compound ,Pyridine ,Molecule ,Infrared multiphoton dissociation ,Physical and Theoretical Chemistry ,Binding site ,Spectroscopy ,Settore CHIM/03 - Chimica Generale e Inorganica ,010405 organic chemistry ,Chemistry ,0104 chemical sciences ,Crystallography ,Quinuclidine - Abstract
We explore the possibility that protonated molecular ions might be an unexpected source of interference in the recognition process of anions and neutral species by Zn-salophen receptors. Zn-salophen complexes are known to bind anions and neutral molecules in solution. We present here evidence (from computational work and IRMPD spectroscopy) that these complexes can also be the binding site for protonated pyridine or quinuclidine. The resulting binding pattern does not involve the Zn ion, but one of the oxygen atoms directly attached to it. The resulting complex therefore turns out to have a positive charge adjacent to the Zn-salophen binding site. This finding seems to point to the existence of an interfering factor in the quantification of the experimental data about the association constant.
- Published
- 2017
46. Unexpected proton mobility in the bulk phase of cholinium-based ionic liquids: new insights from theoretical calculations
- Author
-
Marco Campetella, Lorenzo Gontrani, Eleonora Scarpellini, Enrico Bodo, and Maria Montagna
- Subjects
pseudopotentials ,x-ray-diffraction ,Proton ,Chemistry ,Scattering ,General Physics and Astronomy ,dynamics ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Ab initio molecular dynamics ,chemistry.chemical_compound ,Deprotonation ,Settore CHIM/02 ,Computational chemistry ,Phase (matter) ,Ionization ,Ionic liquid ,amino-acid ,Physical and Theoretical Chemistry ,Proton mobility ,0210 nano-technology - Abstract
We have explored by means of ab initio molecular dynamics two ionic liquids based on the combination of a choline cation with deprotonated cysteine and aspartic acid anions. While the combination of the strong base choline with various other amino-acids leads to the formation of a highly ionized medium where proton transfer is negligible, the presence of additional protic functions on the SH and COOH groups leads to an unexpected and interesting behavior and to a sizable migration of their acidic protons onto the NH2 basic terminals. As far as we know this is the first time that such proton migration, which in water leads to the well-known zwitterionic form of aminoacids, is observed to take place in their ionized, anionic form. We analyze in detail such dynamical effects using accurate ab initio molecular dynamics computations validated through comparison with X-ray scattering data.
- Published
- 2017
47. Adenosine monophosphate recognition by zinc-salophen complexes: IRMPD spectroscopy and quantum modeling study
- Author
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Enrico Bodo, Debora Scuderi, Anna Giardini, Simonetta Fornarini, Gianpiero Forte, Susanna Piccirillo, Alessandra Ciavardini, and Antonella Dalla Cort
- Subjects
chemistry.chemical_classification ,Adenosine monophosphate ,Settore CHIM/03 - Chimica Generale e Inorganica ,spectroscopy ,010405 organic chemistry ,Hydrogen bond ,Stacking ,chemistry.chemical_element ,Aromaticity ,Zinc ,010402 general chemistry ,01 natural sciences ,Atomic and Molecular Physics, and Optics ,0104 chemical sciences ,Nucleobase ,atomic and molecular physics and optics ,Crystallography ,chemistry.chemical_compound ,adenosine. zinc-salophen ,chemistry ,Nucleic acid ,physical and theoretical chemistry ,Nucleotide - Abstract
Zn-salophen complexes are a promising class of fluorescent chemosensors for nucleotides and nucleic acids. We have investigated, by means of IRMPD spectroscopy experiments and quantum chemical calculations, the structure of the host-guest complexes formed by two efficient Zn-salophen receptors and dihydrogen phosphate or adenosine 5′-monophosphate (AMP) anions. In the host-guest complexes the phosphate group is bound with a Zn O(phosphate) bond. In addition, a hydrogen bond can be formed between the PO H group and one of the oxygen atoms of the salophen structure. The complexes with AMP anions are endowed with a hydrogen bonded coordination motif together with a weaker π⋯π interaction. It is thus confirmed that the marked changes of the spectroscopic emission properties of Zn-salophen when complexed with AMP can be associated with the existence of π⋯π stacking interactions between the salophen aromatic rings and those of the adenosine nucleobase.
- Published
- 2017
48. Experimental and DFT/Time‐Dependent DFT Studies on Neutral and One‐Electron‐Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (Pd II , Pt II ) Derivatives
- Author
-
Corrado Rizzoli, Elisa Viola, Luisa Mannina, Maria Pia Donzello, Enrico Bodo, Karl M. Kadish, Giorgia De Mori, David Futur, Claudio Ercolani, Maria Luisa Astolfi, and Zhen Fu
- Subjects
Pyrazine ,chemistry.chemical_element ,Electrochemistry ,Photochemistry ,Spectral line ,Inorganic Chemistry ,chemistry.chemical_compound ,Crystallography ,Ultraviolet visible spectroscopy ,Quinoxaline ,chemistry ,Atomic orbital ,Pyridine ,Platinum - Abstract
Electrochemical and UV/Vis spectral studies on the quinoxaline compound 2,3-di(2-pyridyl)-6,7-dicyano-1,4-quinoxaline, [(CN)2Py2Qx], its metallated derivatives [(CN)2Py2QxMCl2] (M = PdII, PtII) and their analogues sharing the dicyanopyrazine fragment are presented and discussed. X-ray work on the new quinoxaline complex [(CN)2Py2QxPtCl2] establishes that PtII is coordinated to the pyridine N atoms (“py–py” coordination). The spectra of the 1– charged quinoxaline and pyrazine compounds show new intense absorptions in the region of 500–900 nm, and redshifted bands in the 250–400 nm region. By using DFT/time-dependent DFT calculations, the spin density and spectral features of both couples of precursors and PtII derivatives were investigated in terms of single-electron excitations between the Kohn–Sham orbitals of the optimized structures in the gas and condensed phases. A detailed comparison is allowed of the experimental and calculated spectral features of the neutral and 1– charged species.
- Published
- 2014
49. Unravelling the Structure of Protic Ionic Liquids with Theoretical and Experimental Methods: Ethyl-, Propyl- and Butylammonium Nitrate Explored by Raman Spectroscopy and DFT Calculations
- Author
-
Fabio Ramondo, Francesca Ceccacci, Enrico Bodo, Paolo Postorino, and Sara Mangialardo
- Subjects
Chemistry ,Hydrogen bond ,Ab initio ,Structure (category theory) ,Electronic structure ,ionic liquids ,molecular dynamics ,calculations ,Spectral line ,Surfaces, Coatings and Films ,Interpretation (model theory) ,symbols.namesake ,chemistry.chemical_compound ,Computational chemistry ,Ionic liquid ,Materials Chemistry ,symbols ,Physics::Chemical Physics ,Physical and Theoretical Chemistry ,Raman spectroscopy - Abstract
We present an analysis of gas-phase structures of small clusters of n-alkylammonium nitrates (ethyl, propyl, and butyl) together with vibrational Raman spectroscopy of their respective liquid phases. The assignment and interpretation of the resonant frequencies have been performed by comparison with high-quality ab initio (DFT) computations. The theoretical spectra are in excellent agreement with the measured ones and allow the interpretation and assignment of almost all the spectral features. A careful analysis of the vibrational frequencies and of the electronic structure of the compounds has provided additional information on various structural features and on the rather complex hydrogen bonding network that exists in such compounds. A geometric structure of the short-range local arrangement in the bulk phases is also proposed.
- Published
- 2012
50. Structure, Stability, and Electronic Properties of Dimethyl Sulfoxide and Dimethyl Formammide Clusters Containing Th(4.)
- Author
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Enrico Bodo, Riccardo Spezia, Maria Montagna, Yannick Jeanvoine, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR-10-JCJC-0807,ACLASOLV,Solvatation d'actinides et lanthanides(2010), Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome], Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Roma 'La Sapienza' [Rome], Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE - UMR 8587), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Université d'Évry-Val-d'Essonne (UEVE)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine, ANR: ACLASOLV,ANR-2010-JCJC-080701, and Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
- Subjects
C atoms ,Solvation shell ,Electronic structure ,010402 general chemistry ,01 natural sciences ,Dimethyl sulfoxide (DMSO) ,chemistry.chemical_compound ,Oxygen donors ,Computational chemistry ,Atom ,Cluster (physics) ,Molecule ,molecular-dynamics ,hydration structure ,aqueous-solution ,rare-earths ,aqua ions ,complexes ,coordination ,thorium(iv) ,extraction ,separation ,Physical and Theoretical Chemistry ,Electronic properties ,010405 organic chemistry ,Chemistry ,Dimethyl sulfoxide ,Oxygen atom ,Molecules ,0104 chemical sciences ,3. Good health ,Organic solvents ,Density functional theory ,Physical chemistry ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] - Abstract
International audience; By using accurate density functional theory calculations, we have studied the complexes of Th4+ with dimethyl-sulfoxide (DMSO) and dimethyl-formammide (DMF) molecules. These solvents are prototypes for oxygen-donor organic environments in which the oxygen atom is connected to S and C atom, respectively. Extended structural, energetic, and electronic structure analysis has been performed to provide a complete picture of the physical properties at the basis of the interaction of Th4+ with the two solvents. By using a cluster grow approach, we have found that, very likely, the first solvation shell contains nine molecules in the case of DMSO, while it contains eight molecules for DMF. The theoretical results shown here are in agreement with experimental data taken from the literature.
- Published
- 2016
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