NONEQUILIBRIUM SOLVATION - THE MUTUAL INFLUENCE OF SOLUTE AND SOLVENT DYNAMICS

被引：7

作者：

AGUILAR, MA

HIDALGO, A

机构：

[1] Chemical Physics Department, University of Extremadura, Badajoz

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 12期

关键词：

D O I：

10.1021/j100012a061

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A new approach for the study of the mutual influence of solute and solvent dynamics is presented. This method allows one to specify the solute-solvent Hamiltonian using the in vacuo solute potential and the nonequilibrium solvation free energy. A criterion to discard or to take into account the different solvent coordinates, depending on their influence on the solute dynamics, is established. Variational results are obtained using the global (two-dimensional) Hamiltonian and the two one-dimensional limits, SCF and BO. Two typical dynamic processes have been studied, the vibrational motion of a diatomic molecule and a proton transfer reaction in solution.

引用

收藏

页码：4293 / 4305

页数：13

相关论文

共 43 条

[1] CHEMICAL-REACTIONS IN SOLUTION - MODELING OF THE DELAY OF SOLVENT SYNCHRONISM (DIELECTRIC FRICTION) ALONG THE REACTION-PATH OF AN SN2 REACTION [J].

AGUILAR, M ;

BIANCO, R ;

MIERTUS, S ;

PERSICO, M ;

TOMASI, J .

CHEMICAL PHYSICS, 1993, 174 (03) :397-407

[2] NONEQUILIBRIUM SOLVATION - AN ABINITIO QUANTUM-MECHANICAL METHOD IN THE CONTINUUM CAVITY MODEL APPROXIMATION [J].

AGUILAR, MA ;

DELVALLE, FJO ;

TOMASI, J .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (09) :7375-7384

[3] CALCULATION OF THE RATE-CONSTANT FOR THE REACTION CL-+CH3CL -] CLCH3+CL- IN THE FRAMEWORK OF THE CONTINUUM MEDIUM MODEL [J].

BASILEVSKY, MV ;

CHUDINOV, GE ;

NAPOLOV, DV .

JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (13) :3270-3277

[4] APPLICATION OF THE CONFIGURATION-INTERACTION METHOD FOR QUANTUM-CHEMICAL CALCULATIONS OF SOLVATION EFFECTS [J].

BASILEVSKY, MV ;

CHUDINOV, GE ;

NAPOLOV, DV ;

TIMOFEEVA, LM .

CHEMICAL PHYSICS, 1993, 173 (03) :345-355

[5] APPLICATION OF GENERALIZED TRANSITION-STATE THEORY FOR CALCULATION OF THE RATE-CONSTANT OF A CHEMICAL-REACTION WITH CHARGE-TRANSFER IN A POLAR-SOLVENT [J].

BASILEVSKY, MV ;

CHUDINOV, GE .

CHEMICAL PHYSICS, 1990, 144 (02) :155-166

[6] DYNAMICS OF CHARGE-TRANSFER CHEMICAL-REACTIONS IN A POLAR MEDIUM WITHIN THE SCOPE OF THE BORN-KIRKWOOD-ONSAGER MODEL [J].

BASILEVSKY, MV ;

CHUDINOV, GE .

CHEMICAL PHYSICS, 1991, 157 (03) :327-344

[7] ON THE ROLE OF MEDIUM ELECTRONS IN THE OUTER-SPHERE ELECTRON-TRANSFER REACTIONS [J].

BASILEVSKY, MV ;

CHUDINOV, GE .

CHEMICAL PHYSICS, 1992, 165 (2-3) :213-226

[8] NONEQUILIBRIUM SOLVATION IN CHEMICAL-REACTIONS .1. EFFECTIVE EQUATIONS OF MOTION [J].

BEREZHKOVSKII, AM .

CHEMICAL PHYSICS, 1992, 164 (03) :331-339

[9]

BOTTCHER CJF, 1973, THEORY ELECTRIC POLA, V1

[10] SOLVENT REORGANIZATION IN OPTICAL AND THERMAL ELECTRON-TRANSFER PROCESSES - SOLVATOCHROMISM AND INTRAMOLECULAR ELECTRON-TRANSFER BARRIERS IN SPHEROIDAL MOLECULES [J].

BRUNSCHWIG, BS ;

EHRENSON, S ;

SUTIN, N .

JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (18) :4714-4723

← 1 2 3 4 5 →