IMPORTANCE OF FAST SOLVENT RELAXATION COMPONENTS TO ELECTRON-TRANSFER RATES - COMPARISONS BETWEEN BARRIER-CROSSING FREQUENCIES AND SUBPICOSECOND TIME-RESOLVED SOLVATION DYNAMICS

被引：66

作者：

WEAVER, MJ ^{[1
]}

MCMANIS, GE ^{[1
]}

JARZEBA, W ^{[1
]}

BARBARA, PF ^{[1
]}

机构：

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

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1990年 / 94卷 / 05期

关键词：

D O I：

10.1021/j100368a001

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 solvent-dependent barrier-crossing dynamics for outer-sphere electron transfer as derived from metallocene rate and optical barrier data are compared with subpicosecond time-resolved solvation dynamics obtained from time-dependent fluorescence Stokes shifts with coumarin probes. In the majority of cases, especially for propylene carbonate and methanol, the "fast" (≲1 ps) relaxation components identified in the latter measurements appear to provide an important contribution to the barrier-crossing dynamics, although exceptions are also observed. Possible limitations to the influence of additional "fast" solvent relaxation components upon electron-transfer dynamics are briefly discussed. © 1990 American Chemical Society.

引用

页码：1715 / 1719

页数：5

共 40 条

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