Electronic excitation energies, three-state intersections, and photodissociation mechanisms of benzaldehyde and acetophenone

被引：30

作者：

Cui, Ganglong ^{[1
]}

Lu, You ^{[1
]}

Thiel, Walter ^{[1
]}

机构：

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

来源：

CHEMICAL PHYSICS LETTERS | 2012年 / 537卷

关键词：

MULTIREFERENCE PERTURBATION-THEORY; ABSORPTION CROSS-SECTIONS; AROMATIC CARBONYL-COMPOUNDS; RELAXATION DYNAMICS; BENZOIC-ACID; SPECTRA; STATES; NM; UV;

D O I：

10.1016/j.cplett.2012.04.008

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 a theoretical study on the electronically excited states and the mechanisms of photodissociation of C6H5CHO and C6H5COCH3. For both molecules, we find an S-1/T-2/T-1 three-state intersection region, which allows for an efficient S-1 -> T-1 intersystem crossing via the T-2 state that acts as a relay. Consequently, T-1 reactions become the major radical photodissociation channels. According to the computed energy profiles, T-1 photodissociation mainly yields phenyl and formyl radicals in the case of benzaldehyde, and benzoyl and methyl radicals in the case of acetophenone, with different C-C bonds being cleaved preferentially. The computational results agree well with the available experimental data. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：21 / 26

页数：6

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