State correlations in the unimolecular dissociation of ketene

被引:17
作者
Costen, ML
Katayanagi, H
Hall, GE [1 ]
机构
[1] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
[2] Inst Mol Sci, Okazaki, Aichi 4448585, Japan
关键词
D O I
10.1021/jp001389f
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
Doppler-broadened absorption spectra of selected rotational levels of singlet CH2 fragments from the 308-nm photolysis of ketene have been observed by frequency-modulated transient absorption spectroscopy in a slit jet expansion. Nascent Doppler profiles of CH2 transitions have been analyzed to yield the internal energy distributions of coincident CO fragments at a total energy 2333 cm(-1) above the singlet dissociation threshold. The vibrational branching ratio of CO (v = 1):(v = 0) is determined in coincidence with selected rotational levels of CH2. The coincident rotational distributions of CO (v = 0) are also estimated and found to differ from simple statistical predictions, revealing a relative deficiency of those pairs in which both fragments have a low internal energy.
引用
收藏
页码:10247 / 10258
页数:12
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