Femtosecond real-time probing of reactions .20. Dynamics of twisting, alignment, and IVR in the trans-stilbene isomerization reaction

被引：122

作者：

Baskin, JS ^{[1
]}

Banares, L ^{[1
]}

Pedersen, S ^{[1
]}

Zewail, AH ^{[1
]}

机构：

[1] CALTECH,ARTHUR AMOS NOYES LAB CHEM PHYS,PASADENA,CA 91125

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1996年 / 100卷 / 29期

关键词：

D O I：

10.1021/jp960909x

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：

The femtosecond real-time dynamics of the isomerization reaction of trans-stilbene under collisionless conditions are studied using (2+1) resonance-enhanced multiphoton ionization (REMPI) and femtosecond depletion spectroscopy (FDS) in a pump-probe scheme. The observed transients reflect the macroscopic sample anisotropy decay (rotational coherence) and intramolecular vibrational energy redistribution (IVR) as well as the ethylenic twisting isomerization reaction. Polarization-resolved measurements are performed to isolate the influence of rotational dynamics, and the measured anisotropy decay is compared with theoretical calculations of rotational coherence at room temperature. The IVR and nonradiative (isomerization) processes of trans-stilbene are studied as a function of S-1 excess vibrational energy up to similar to 6500 cm(-1). These results are compared with previous measurements of trans-stilbene under collisionless conditions and with predictions of RRK and RRKM theories.

引用

页码：11920 / 11933

页数：14

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