INTERPLAY OF SOLVENT MOTION AND VIBRATIONAL-EXCITATION IN ELECTRON-TRANSFER KINETICS - EXPERIMENT AND THEORY

被引：331

作者：

WALKER, GC ^{[1
]}

AKESSON, E ^{[1
]}

JOHNSON, AE ^{[1
]}

LEVINGER, NE ^{[1
]}

BARBARA, PF ^{[1
]}

机构：

[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1992年 / 96卷 / 09期

关键词：

D O I：

10.1021/j100188a032

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：

This paper reports new kinetic data on the electron-transfer kinetics of betaine-30 and the related compound tert-butylbetaine. The experimental data are in excellent agreement with a new theoretical model which is an extension of the approach given by Sumi and Marcus (Sumi, H; Marcus, R. A. J. Chem. Phys. 1986, 84, 4894). Most of the parameters required for the kinetic predictions can be obtained in a straightforward fashion by fitting the static absorption spectra of the charge-transfer band. The combined theoretical and experimental results demonstrate that an accurate model for electron transfer in the inverted regime in solution minimally requires the following three nuclear degrees of freedom: (i) a solvent mode with a frictional response, (ii) an intramolecular low-frequency (classical) mode, and (iii) a high-frequency (quantum mechanical) intramolecular mode. Furthermore, the analysis allows for a detailed understanding of the combined effects of solvation dynamics and vibrational excitations in ultrafast electron-transfer kinetics.

引用

页码：3728 / 3736

页数：9

共 25 条

[1] DYNAMIC SOLVENT EFFECTS ON ELECTRON-TRANSFER RATES IN THE INVERTED REGIME - ULTRAFAST STUDIES ON THE BETAINES [J].