FEMTOSECOND STUDIES OF THE IODINE-MESITYLENE CHARGE-TRANSFER COMPLEX

被引:29
作者
PULLEN, S
WALKER, LA
SENSION, RJ
机构
[1] Department of Chemistry, University of Michigan, Ann Arbor
关键词
D O I
10.1063/1.470205
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
Femtosecond laser studies have been performed to investigate the initial photodissociation reactions of I-2-mesitylene charge transfer complexes. Photodissociation occurs along both the I-2-mesitylene ''bond'' and the I-I bond with a branching ratio of 2:3 for the two reaction coordinates. Following excitation at 400 nm, geminate recombination occurs along both reaction coordinates. The reformed I-2-mesitylene complexes are formed vibrationally hot and relax on a time scale of 13 ps. The I-mesityfene spectrum is fully developed within 500 fs of the pump pulse. Approximately 40% of the I-mesitylene complexes undergo geminate recombination on a time scale of 14 ps. Most of the remaining complexes recombine with their original partners on a time scale of 400 ps. The initial anisotropy of the photoproduct absorption is 0.09+/-0.02. This low anisotropy is a direct result of the geometry of the complex and nature of the electronic transition rather than indicative of ultrafast motion toward an asymmetric transition state preceding dissociation. (C) 1995 American Institute Physics.
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页码:7877 / 7886
页数:10
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