SOLVATION EFFECTS ON REACTIVE INTERMEDIATES - THE BENZYL RADICAL AND ITS CLUSTERS WITH AR, N2, CH4, C2H6, AND C3H8

被引:38
作者
DISSELKAMP, R
BERNSTEIN, ER
机构
[1] Chemistry Department, Colorado State University, Fort Collins
关键词
D O I
10.1063/1.464996
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
Mass resolved excitation spectra are presented for the benzyl radical and its clusters with Ar, N2, CH4, C2H6, and C3H8. The cluster spectra exhibit small redshifts (< 50 cm-1) relative to the unclustered benzyl radical for the D1(1(2)A2) <-- D0(1(2)B2) and D2(2(2)B2) <-- D0(1(2)B2) electronic transition regions. A unique set of low energy van der Waals modes is observed for these clusters for each excited electronic state investigated. The cluster spectra also reveal significant vibronic coupling between the two excited electronic states of the benzyl radical, as evidenced by a single vibrational predissociation threshold for each cluster. Ab initio calculations are performed on the benzyl radical to examine excited electronic state structure, predict transition energies, estimate ionization energy, and determine partial atomic charges in the electronic states of interest. The resulting partial charges are used in empirical atom-atom potential energy calculations to aid in the understanding of cluster spectroscopic shifts, binding energies, and van der Waals modes.
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收藏
页码:4339 / 4354
页数:16
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