HOX(X=F,Cl)二聚体红移氢键的理论研究  

Theoretical study of hydrogen bond red-shifting in the HOX(X=F,Cl)dimers

作　　者：张先燚[1] 张培[1] 肖伟[1] 汪飞[1] 崔执凤[1] 

机构地区：[1]安徽师范大学物理与电子信息学院,芜湖241000

出　　处：《原子与分子物理学报》2009年第2期202-208,共7页Journal of Atomic and Molecular Physics

基　　金：安徽省高等学校优秀青年教师基金(2004jq117);安徽省原子与分子物理重点学科基金

摘　　要：用理论方法研究了二聚体HOX(X=F,Cl)分子间氢键,在B3LYP/6-31+G(d,p)、B3LYP/6-311++G(d,p)、MP2/6-31+G(d,p)和MP2/6-311++G(d,p)水平上,利用标准方法和均衡校正方法对二聚体进行了几何优化、振动频率和相互作用能的计算.同时,利用电子密度拓扑分析和自然键轨道分析对红移氢键的本质进行了分析.研究表明:分子间O—H…O和O—H…X(X=F,Cl)氢键的形成使二聚体中O—H键伸长,伸缩振动频率减小,形成红移氢键.NBO分析表明,电荷转移效应占优势,因此形成O—H…O和O—H…X(F,Cl)红移氢键.Theoretical calculations were performed to study the hydrogen bond in the HOX(X=F,Cl) dimer. Using B3LYP/6-31 + G(d,p), B3LYP/6-311 + + G(d,p) , MP2/6-31 + G(d,p) and MP2/6-311 + + G(d,p) , the geometric structures, vibrational frequencies and interaction energies were calculated by both standard and CP-corrected methods. In additions, the origin of the red-shift hydrogen bond were discussed through the topological and NBO analysis. The results indicated that in the formation of hydrogen bond O—H…O and O—H…X(X=F,C1) , the bond O—H in the dimer is lengthened, symmetry vibrational frequencies decreases, leading to the red-shifting. From the NBO analysis, the red-shifted hydrogen bond O—H…O and O—H…X(F, Cl) is formed due to the charge transfer effect.

关 键 词：红移氢键 拓扑分析 自然键轨道分析 

分 类 号：O643[理学—物理化学]