Ultrafast Dynamics of UV-Excited Imidazole

被引：32

作者：

Crespo-Otero, Rachel ^{[1
]}

Barbatti, Mario ^{[1
]}

Yu, Hui ^{[2
]}

Evans, Nicholas L. ^{[2
]}

Ullrich, Susanne ^{[2
]}

机构：

[1] Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany

[2] Univ Georgia, Dept Phys & Astron, Athens, GA 30602 USA

来源：

CHEMPHYSCHEM | 2011年 / 12卷 / 17期

基金：

美国国家科学基金会;

关键词：

femtochemistry; imidazole; molecular dynamics; photochemistry; photoelectron spectroscopy; MOLECULAR-DYNAMICS; NONADIABATIC DYNAMICS; PHOTOELECTRON-SPECTROSCOPY; CONICAL INTERSECTIONS; BASIS-SETS; PHOTOCHEMISTRY; APPROXIMATION; DEACTIVATION; EXCITATIONS; RELAXATION;

D O I：

10.1002/cphc.201100453

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 ultrafast dynamics of UV-excited imidazole in the gas phase is investigated by theoretical nonadiabatic dynamics simulations and experimental time-resolved photoelectron spectroscopy. The results show that different electronic excited-state relaxation mechanisms occur, depending on the pump wavelength. When imidazole is excited at 239.6 nm, deactivation through the NH-dissociation conical intersection is observed on the sub-50 fs timescale. After 200.8 nm excitation, competition between NH-dissociation and NH-puckering conical intersections is observed. The NH-dissociation to NH-puckering branching ratio is predicted to be 21:4, and the total relaxation time is elongated by a factor of eight. A procedure for simulation of photoelectron spectra based on dynamics results is developed and employed to assign different features in the experimental spectra.

引用

页码：3365 / 3375

页数：11

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