NONEQUILIBRIUM FREE-ENERGY FUNCTIONS, RECOMBINATION DYNAMICS, AND VIBRATIONAL-RELAXATION OF I2- IN ACETONITRILE - MOLECULAR-DYNAMICS OF CHARGE FLOW IN THE ELECTRONICALLY ADIABATIC LIMIT

被引:96
作者
BENJAMIN, I
BARBARA, PF
GERTNER, BJ
HYNES, JT
机构
[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455
[2] UNIV COLORADO,DEPT CHEM & BIOCHEM,BOULDER,CO 80309
关键词
D O I
10.1021/j100019a042
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
The recombination and vibrational relaxation of I-2(-) in acetonitrile is investigated using molecular dynamics computer simulation. The change in the solute electronic structure during the reaction is explicitly taken into account in the electronically adiabatic limit. The nonequilibrium free energy surface describing the transition from delocalized charge distribution (I-2(-)) at a small internuclear distance (r) to a localized charge distribution (I + I-) at large r is calculated using umbrella sampling from the microscopic electronically adiabatic Hamiltonian. This Hamiltonian is used to calculate vibrational relaxation and recombination efficiency in reasonable agreement with experimental results. It is found that the additional force along the vibrational coordinate r due to the shifting charge distribution, i.e., charge flow, accelerates the vibrational relaxation rate.
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页码:7557 / 7567
页数:11
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