SUBPICOSECOND RESOLUTION STUDIES OF THE H+CO2-]CO+OH REACTION PHOTOINITIATED IN CO2-HI COMPLEXES

被引:97
作者
IONOV, SI
BRUCKER, GA
JAQUES, C
VALACHOVIC, L
WITTIG, C
机构
[1] Department of Chemistry, University of Southern California, Las Angeles
[2] Stanford Research Systems, Sunnyvale, CA 94089
关键词
D O I
10.1063/1.465847
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
Time resolved studies of the title reaction have been carried out by photodissociating the HI moiety within weakly bound CO2-HI complexes. The HOCO(dagger) intermediate decomposes via a unimolecular decomposition mechanism, and the emerging hydroxyl radicals are monitored with subpicosecond temporal resolution by using laser-induced fluorescence. The measured rates are in good agreement with several theoretical predictions: Rice, Ramsperger, Kassel, and Marcus (RRKM) calculations; classical trajectory simulations on the best available potential energy surface; and recent quantum scattering calculations.
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页码:6553 / 6561
页数:9
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