CH_3SH和CH_3SLi分子间的锂键和氢键共存型相互作用  

Co-Existing Lithium Bonding and Hydrogen Bonding Interactions between CH_3SH and CH_3SLi

作　　者：刘艳芝[1] 施小宁[1] 唐慧安[1] 刘新文[1] 袁焜[1] 张俊彦[2] 张继[3] 

机构地区：[1]天水师范学院生命科学与化学学院,天水741001 [2]中国科学院兰州化学物理研究所,兰州730000 [3]西北师范大学生命科学学院,兰州730000

出　　处：《化学学报》2010年第6期493-500,共8页Acta Chimica Sinica

基　　金：天水师范学院"青蓝"人才工程基金;甘肃省教育厅研究生导师科研基金(No.07-08-12)资助项目

摘　　要：在CH3SLi+CH3SH势能面上求得锂键和氢键共存型复合物的两种稳定构型.频率分析表明,与单体相比复合物中S(5)—Li(6)键伸缩振动频率发生红移,而C(8)—H(10)键伸缩振动频率发生蓝移.经B3LYP/6-311++G**,MP2/6-311++G**及MP2/AUG-CC-PVDZ水平计算的含基组重叠误差(BSSE)校正的复合物Ⅰ中相互作用能分别为-58.99,-57.87和-62.89kJ·mol-1.采用自然键轨道(NBO)理论,分析了复合物中单体轨道间的电荷转移,电子密度重排及其与相关键键长变化的本质等.采用分子中的原子(AIM)理论分析了复合物中氢键和锂键的电子密度拓扑性质.在极化连续模型(PCM)下,考察了溶剂化效应.结果表明,所考察的水、二甲亚砜、乙醇和乙醚等四种溶剂均使单体间的相互作用能增大,且溶剂对复合物中的锂键结构及其振动频率具有显著的影响,而对复合物中的氢键的振动频率影响不大.The two optimized stable lithium bonding and hydrogen bonding co-existing complexes, CH3SLi…CH3SH, were found on the potential energy surface of CH3SLi＋CH3SH. Red shift of the S（5）— Li（6） and blue shift of C（8）—H（10） stretching vibrational frequencies were obtained simultaneously via frequency analysis. The BSSE-corrected interaction energies in complex Ⅰ obtained by using B3LYP/6-311＋ ＋G^＊＊, MP2/6-311＋＋G^＊＊ and MP2/AUG-CC-PVDZ were-58.99, -57.87 and -62.89 kJ·mol^-1, respectively. From the natural bond orbital （NBO） analysis, The charge transfer interactions between the related orbits, electron density redistributions and the essential of the correlative bond length changes in the complexes were detailedly discussed. The topological properties of the hydrogen bond and lithium bond structures were also investigated by the atoms-in-molecules （AIM） theory. In addition, the solvent effects were studied using the polarized continuum model （PCM）. The results showed that the interaction energy would increase in the presence of solvents, and the solvents could evidently affect the geometric structure and vibration frequency of the lithium bond in CH3SLi…CH3SH, but not obviously the frequency of the hydrogen bond.

关 键 词：甲硫醇锂 氢键和锂键共存 自然键轨道理论 分子中原子理论 溶剂化效应 

分 类 号：O641.1[理学—物理化学]