Photoinduced disruption of the strong intramolecular H-bond in the enol form of acetylacetone: Mechanisms of radiationless decay

被引：0

作者：

Delchev, Vassil B. ^{[1
]}

Shterev, Ivan G. ^{[2
]}

机构：

[1] Paisij Hilendarski Univ Plovdiv, Dept Phys Chem, BG-4000 Plovdiv, Bulgaria

[2] Univ Food Technol, Dept Inorgan & Phys Chem, Plovdiv 4002, Bulgaria

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2011年 / 967卷 / 01期

关键词：

Acetylacetone; CC2; method; Conical intersections; Excited states; Linear interpolation; SELF-CONSISTENT-FIELD; MATRIX-ISOLATION; EXCITED-STATES; UV; EQUILIBRIUM; RESOLUTION; CC2;

D O I：

10.1016/j.comptc.2011.04.009

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 propose mechanisms which describe the photoinduced disruption of the intramolecular H-bond in the stable enol form of acetylacetone. The study was performed with the second-order approximate coupled cluster singles and doubles model CC2. The basis set aug-cc-pVDZ was applied. The excited-state reaction paths of the rotations around C-C, C=C and C-O bonds were investigated using both coordinate-driven (relaxed scan) and linear interpolation in internal coordinates (LIIC) approaches. We show that the (1)pi pi* excited states of the rotations around the C=C double bond relax in, a completely barrierless manner, to the ground state via S-0-S-1 conical intersections. This is the main relaxation channel of the excited states associated with the disruption of the strong H-bond in the enol form of acetylacetone. The C-C and C-O rotations did not show such mechanisms. (C) 2011 Elsevier B.V. All rights reserved.

引用

页码：152 / 159

页数：8

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