SOLVATION ENERGY OF NONEQUILIBRIUM POLARIZATION: OLD QUESTION, NEW ANSWER-Reference-Cited by-同舟云学术

SOLVATION ENERGY OF NONEQUILIBRIUM POLARIZATION: OLD QUESTION, NEW ANSWER

Published:2010-01 Issue:supp01 Volume:09 Page:23-37
ISSN:0219-6336
Container-title:Journal of Theoretical and Computational Chemistry
language:en
Short-container-title:J. Theor. Comput. Chem.

Author:

LI XIANG-YUAN¹,HE FU-CHENG¹,FU KE-XIANG¹,LIU WENJIAN²³

Affiliation:

1. College of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China

2. Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, P. R. China

3. Center for Computational Science and Engineering, Peking University, Beijing 100871, P. R. China

Abstract

Although an old question, the electrostatic free energy of nonequilibrium solvation in a continuous dielectric has recently been disputed. Here we show that the nonequilibrium solvation energy can be obtained without any ambiguity by imposing a suitable external electric field with its source localized in the ambient so as to bring the nonequilibrium into an equilibrium state but constrain its charge distribution, polarization, and entropy unchanged. As an application, a two-sphere cavity model is proposed for estimating the solvent reorganization energy, which solves the longstanding issue that it tends to be overestimated by a factor of two by the popular continuum models.

Publisher

World Scientific Pub Co Pte Lt

Subject

Computational Theory and Mathematics,Physical and Theoretical Chemistry,Computer Science Applications

Link

https://www.worldscientific.com/doi/pdf/10.1142/S0219633610005591

Reference28 articles.

1. Quantum Mechanical Continuum Solvation Models

2. Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. I

3. On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I

4. Reorganization Energy for Electron Transfer at Film-Modified Electrode Surfaces: A Dielectric Continuum Model

5. Free Energy of Nonequilibrium Polarization Systems. 4. A Formalism Based on the Nonequilibrium Dielectric Displacement

Cited by 19 articles. 订阅此论文施引文献订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献

1. Solvent effects for vertical absorption and emission processes in solution using a self-consistent state specific method based on constrained equilibrium thermodynamics;Physical Chemistry Chemical Physics;2018

2. Novel nonequilibrium solvation theory for calculating the vertical ionization energies of alkali metal cations and DNA bases in aqueous;Theoretical Chemistry Accounts;2017-12-11

3. Theoretical study on electronic excitation spectra: A matrix form of numerical algorithm for spectral shift;Chemical Physics;2017-07

4. Solvent effects on excitation energies obtained using the state-specific TD-DFT method with a polarizable continuum model based on constrained equilibrium thermodynamics;Physical Chemistry Chemical Physics;2017

5. Nonequilibrium Solvation Theory Based on Constrained Equilibrium Principle and Its Applications;CHEM J CHINESE U;2015