A statistical thermodynamics view of electron density polarisation: application to chemical selectivity
A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. From a more detailed analysis of the heat exchange in a perturbation...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2020-10, Vol.22 (41), p.23553-23562 |
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| container_title | Physical chemistry chemical physics : PCCP |
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| creator | Guégan, Frédéric Tognetti, Vincent Martínez-Araya, Jorge I Chermette, Henry Merzoud, Lynda Toro-Labbé, Alejandro Morell, Christophe |
| description | A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. From a more detailed analysis of the heat exchange in a perturbation theory framework, an associated entropy can be subsequently derived, which appears to be a suitable descriptor for the local polarisability of the electron density. A general rule of thumb is evidenced: the more the perturbation can be spread, both through space and among the excited states, the larger the heat exchange and entropy.
A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. |
| doi_str_mv | 10.1039/d0cp03228j |
| format | Article |
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| ispartof | Physical chemistry chemical physics : PCCP, 2020-10, Vol.22 (41), p.23553-23562 |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Chemical Sciences Density functional theory Electron density Entropy Heat exchange or physical chemistry Perturbation theory Selectivity Statistical thermodynamics Theoretical and |
| title | A statistical thermodynamics view of electron density polarisation: application to chemical selectivity |
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