Electron transfer rates from vibrational quantum states

被引:38
作者
Spears, KG
Wen, XN
Zhang, RH
机构
[1] Department of Chemistry, Northwestern University, Evanston
关键词
D O I
10.1021/jp960444a
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
Electron transfer involves changes in molecular geometry that are important for controlling rates. In this work we report the first clear effects of vibrational quantum state on solution phase electron transfer rates. The spontaneous electron transfer rates for the recovery of an ion pair [Co(Cp)(2)(+)/V(CO)(6)(-)] are studied with picosecond infrared spectroscopy following optical excitation into its charge transfer band. The rates increase about 2-fold for each additional vibrational quantum in the CO stretching mode. These results allow new tests of electron transfer theory.
引用
收藏
页码:10206 / 10209
页数:4
相关论文
共 20 条
[1]   ULTRAFAST INFRARED-SPECTROSCOPY OF VIBRATIONAL CO-STRETCH UP-PUMPING AND RELAXATION DYNAMICS OF W(CO)(6) [J].
ARRIVO, SM ;
DOUGHERTY, TP ;
GRUBBS, WT ;
HEILWEIL, EJ .
CHEMICAL PHYSICS LETTERS, 1995, 235 (3-4) :247-254
[2]   CRYSTAL AND MOLECULAR-STRUCTURE OF VANADIUM HEXACARBONYL [J].
BELLARD, S ;
RUBINSON, KA ;
SHELDRICK, GM .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1979, 35 (FEB) :271-274
[3]   CHARGE-TRANSFER ION-PAIRS - STRUCTURE AND PHOTOINDUCED ELECTRON-TRANSFER OF CARBONYLMETALATE SALTS [J].
BOCKMAN, TM ;
KOCHI, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (13) :4669-4683
[4]   PICOSECOND INFRARED STUDY OF ULTRAFAST ELECTRON-TRANSFER AND VIBRATIONAL-ENERGY RELAXATION IN A MIXED-VALENT RUTHENIUM DIMER [J].
DOORN, SK ;
STOUTLAND, PO ;
DYER, RB ;
WOODRUFF, WH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (08) :3133-3134
[5]   PRERESONANCE RAMAN STUDIES OF METAL-TO-LIGAND CHARGE-TRANSFER IN (NH3)4RU(2,2'-BPY)2+ - INSITU BOND LENGTH CHANGES, FORCE-CONSTANTS, AND REORGANIZATION ENERGIES [J].
DOORN, SK ;
HUPP, JT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (13) :4704-4712
[6]   POPULATION RELAXATION OF CO(V=1) VIBRATIONS IN SOLUTION PHASE METAL-CARBONYL-COMPLEXES [J].
HEILWEIL, EJ ;
CAVANAGH, RR ;
STEPHENSON, JC .
CHEMICAL PHYSICS LETTERS, 1987, 134 (02) :181-188
[7]   ELECTRON TRANSFERS IN CHEMISTRY AND BIOLOGY [J].
MARCUS, RA ;
SUTIN, N .
BIOCHIMICA ET BIOPHYSICA ACTA, 1985, 811 (03) :265-322
[9]  
MARCUS RA, 1965, ANNU REV PHYS CHEM, V43, P155
[10]   MODE-SPECIFIC VIBRATIONAL REORGANIZATION ENERGIES ACCOMPANYING PHOTOINDUCED ELECTRON-TRANSFER IN THE HEXAMETHYLBENZENE TETRACYANOETHYLENE CHARGE-TRANSFER COMPLEX [J].
MARKEL, F ;
FERRIS, NS ;
GOULD, IR ;
MYERS, AB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (15) :6208-6219