Addition complexes of dimethyl sulfide (DMS) and OH radical and their reactions with O2 by ab initio and density functional theory

被引:33
|
作者
Wang, LM
Zhang, JS [1 ]
机构
[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA
[2] Univ Calif Riverside, Air Pollut Res Ctr, Riverside, CA 92521 USA
来源
基金
美国国家科学基金会;
关键词
dimethyl sulfide; ab initio; addition complex; 2c-3e bonding;
D O I
10.1016/S0166-1280(00)00866-6
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
Two weakly bound complexes between CH3SCH3 (DMS) and OH, via 2-center-3-electron (2c-3e) bonding and dipole-dipole interaction, have been identified by density functional theory (DFT-B3LYP). The 2c-3e bonding complex is more stable at Gaussian-2 level with -31 kJ/mol relative to DMS+OH. Similar structures are found for the complex of CH3SH with OH. Subsequent reaction of the 2c-3e DMS OH adduct with O-2 is also studied by DFT. A complex between the DMS-OH adduct and O-2 with a strong S-O single bond characteristic is identified. Dissociation or H-atom abstraction of this complex could lead to the formation of (CH3)(2)SO. (C) 2001 Elsevier Science B.V. All rights reserved.
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页码:167 / 175
页数:9
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