A new potential model for acetonitrile: Insight into the local structure organization
| Autor: | Oleg N. Kalugin, Oleksandr M. Korsun, Volodymyr A. Koverga, Abdenacer Idrissi, Bogdan A. Marekha |
|---|---|
| Přispěvatelé: | Department of Inorganic Chemistry, V.N. Karazin Kharkiv National University (KhNU), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL)-Institut de Chimie du CNRS (INC)-Université de Lille |
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
Hydrogen
chemistry.chemical_element 010402 general chemistry 01 natural sciences Force field (chemistry) k-nearest neighbors algorithm Kirkwood factor chemistry.chemical_compound Computational chemistry 0103 physical sciences Materials Chemistry Molecule Physical and Theoretical Chemistry Physics::Chemical Physics Acetonitrile Spectroscopy Potential model 010304 chemical physics Hydrogen bond Condensed Matter Physics Atomic and Molecular Physics and Optics 0104 chemical sciences Electronic Optical and Magnetic Materials [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Dipole chemistry Chemical physics Local structure Nearest neighbor approach Methyl group |
| Zdroj: | Journal of Molecular Liquids Journal of Molecular Liquids, Elsevier, 2017, 233, pp.251-261. ⟨10.1016/j.molliq.2017.03.025⟩ Journal of Molecular Liquids, 2017, 233, pp.251-261. ⟨10.1016/j.molliq.2017.03.025⟩ |
| ISSN: | 0167-7322 |
| DOI: | 10.1016/j.molliq.2017.03.025⟩ |
| Popis: | International audience; Thorough understanding of the microscopic organization and dynamics of individual constituents is a crucial step in the description and the prediction the properties of electrolyte solutions based on dipolar aprotic solvents such as acetonitrile. For this aim, a new potential (force field) model for acetonitrile was developed on the basis of comprehensive approach comprising quantum chemical calculations, ab initio molecular dynamics simulations and empirical parameterization. The developed potential model is able to reproduce the experimental thermodynamic and dynamic properties of neat acetonitrile in the range of temperatures between 228.15 and 348.15 K. The local structure of neat liquid acetonitrile then was analyzed in a framework of the nearest neighbor approach. It was shown that the distance standard deviations relative to the average distance between the nearest neighbors have a non-linear behavior that was traced back to the changes in the mutual orientation between acetonitrile molecules. The closest neighbors have a dominant antiparallel dipoles orientation with respect to a reference acetonitrile molecule, while for the further nearest neighbors perpendicular and parallel mutual orientation is observed. The nearest neighbors approach in combination with angular distribution functions was used for the estimation of the Kirkwood factor. Our results show that in order to reproduce the corresponding experimental values derived in the framework of the Onsager-Kirkwood-Fröhlich theory, it is necessary to take into account the mutual orientation of the 5–6 nearest neighbors. Although the atomic charges, on N and the methyl group hydrogen atoms, are negative, the values of the N ⋯ H distance and the N ⋯ H–C (methyl group), are compatible with a weak hydrogen bond between the two atoms. |
| Databáze: | OpenAIRE |
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