(CH_3)_2S与HOCl分子间的卤键和氢键相互作用  

Halogen Bond and Hydrogen Bond Interactions between (CH_3)_2S and HOCl

作　　者：袁焜[1] 刘艳芝[1] 吕玲玲[1] 马伟超[1] 

机构地区：[1]天水师范学院生命科学与化学学院,甘肃天水741001

出　　处：《物理化学学报》2008年第7期1257-1263,共7页Acta Physico-Chimica Sinica

基　　金：甘肃省教育厅研究生导师科研基金(07-08-12)资助项目

摘　　要：在DFT-B3LYP/6-311++G**水平上分别求得(CH3)2S…ClOH卤键复合物和(CH3)2S…HOCl氢键复合物势能面上的稳定构型.频率分析表明,与单体HOCl相比,在两种复合物中,10Cl—11O和12H—11O键伸缩振动频率发生显著的红移.经MP2/6-311++G**水平计算的含基组重叠误差(BSSE)校正的气相中相互作用能分别为-11.69和-24.16kJ·mol-1.自然键轨道理论(NBO)分析表明,在(CH3)2S…ClOH卤键复合物中,引起10Cl—11O键变长的因素包括两种电荷转移:(i)孤对电子LP(1S)1→σ*(10Cl—11O);(ii)孤对电子LP(1S)2→σ*(10Cl—11O),其中孤对电子LP(1S)2→σ*(10Cl—11O)转移占主要作用,总的结果是使σ*(10Cl—11O)的自然布居数增加0.14035e,同时11O原子的再杂化使其与10Cl成键时s成分增加,即具有与电荷转移作用同样的"拉长效应";在(CH3)2S…HOCl氢键复合物中也存在类似的电荷转移,但是11O原子的再杂化不同于前者.自然键共振理论(NRT)进行键序分析表明,在卤键复合物和氢键复合物中,10Cl—11O和12H—11O键的键序都减小.通过分子中原子理论(AIM)分析了复合物中卤键和氢键的电子密度拓扑性质.The optimized stable （CH3）2S…ClOH halogen bond and （CH3）2S…HOCl hydrogen bond complexes were found on the potential energy surface by means of DFF-B3LYP/6-311＋＋G＊＊. The obvious red shifts of the 10Cl--11O and 12H-11O stretching vibrational frequencies in the two complexes were obtained via frequency analysis. The halogen bond interaction energy of （CH3）2S…ClOH was -11.69 kJ·mol^-1, and the hydrogen bond interaction energy of （CH3）2S…HOCl was -24.16 kJ·mol^-1, which were calculated with basis set superposition error （BSSE） correction via counterpoise procedure （CP） method at MP2/6-311G＊＊ level. Natural bond orbital （NBO） theory analysis showed that two kinds of charge transfers existed in （CH3）2S…ClOH halogen bond system： （i） lone pair LP（1S）^1→σ＊（10CI-11O）; （ii） lone pair LP（1S）^2→σ＊（10Cl-11O）, and the natural population of the σ＊（10Cl--11O） increased by 0.14035e. Analogous charge transfers existed in （CH3）2S…HOCl hydrogen bond complex. Bond order analysis with natural resonance theory （NRT） showed that bond order of 10Cl--11O in （CHz）2S…ClOH halogen bond complex and bond order of 12H-11O in （CH3）2S…HOCl hydrogen bond complex both decreased. The topological properties of the halogen bond and hydrogen bond structures were also investigated by the atoms-in-molecules （AIM） theory.

关 键 词：二甲基硫 次氯酸 卤键复合物 自然键轨道理论 分子中原子理论 

分 类 号：O641.12[理学—物理化学]