Theoretical study of the extremely small torsional barriers of thiophenol in the ground and the first excited electronic states

被引：12

作者：

Choi, Heechol ^{[1
]}

Park, Young Choon ^{[1
]}

Lee, Yoon Sup ^{[1
]}

An, Heesun ^{[2
]}

Baeck, Kyoung Koo ^{[2
]}

机构：

[1] Korea Adv Inst Sci & Technol, Dept Chem, Taejon 305701, South Korea

[2] Gangneung Wonju Natl Univ, Dept Chem, Kangnung 210702, South Korea

来源：

CHEMICAL PHYSICS LETTERS | 2013年 / 580卷

关键词：

MULTIREFERENCE PERTURBATION-THEORY; INTERNAL-ROTATION; DENSITY FUNCTIONALS; PHOTODISSOCIATION; THERMOCHEMISTRY; BENZENETHIOL; DERIVATIVES; CHARACTER; CLUSTERS; PHENOL;

D O I：

10.1016/j.cplett.2013.06.056

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 extremely small (around 0.80 kcal/mol) barrier for the -SH rotation of thiophenol is studied by using MP2, CASSCF(12,11), and three DFT (B3LYP, HCTH, and omega B97X-D) methods with various basis sets. The 6-311++G(3df,3pd) turns out to be the proper minimal basis-set for reliable calculations. CCSD(T) and CASPT2//CASSCF calculations confirm that the planar conformation of the -SH is the minimum-energy structure of not only the ground So but also the first excited S-1 electronic states. The calculated torsional barrier of the S-1, 1.89 kcal/mol, is also quite small. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：32 / 36

页数：5

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