Time- and frequency-resolved photoionisation of the allyl radical

被引:34
作者
Schultz, T [1 ]
Clarke, JS [1 ]
Gilbert, T [1 ]
Deyerl, HJ [1 ]
Fischer, I [1 ]
机构
[1] Swiss Fed Inst Technol, Organ Chem Lab, CH-8092 Zurich, Switzerland
基金
中国国家自然科学基金;
关键词
D O I
10.1039/a909276e
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
We report picosecond time-resolved pump-probe photoelectron spectra of the allyl radical, C3H5, and the fully deuterated allyl, C3D5, carried out in order to elucidate the primary photophysical processes upon UV excitation. It is shown that the UV bands of allyl decay in a two-step process: the first step is an internal conversion to the lower-lying A-state within 20 ps or less, while the second step is a very fast decay from the A-state to the electronic ground state through a conical intersection. In addition we report the first zero kinetic energy (ZEKE) photoelectron spectrum of allyl, yielding an ionisation energy of 65762 cm(-1).
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页码:17 / 31
页数:15
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