HCHO与HNO二聚体、三聚体蓝移氢键的研究  

On Blue Shifting H-Bonds in Dimmers and Tripolymers of HCHO and HNO

作　　者：倪杰[1] 黎安勇[2] 

机构地区：[1]西南林业大学环境科学与工程学院,昆明650224 [2]西南大学化学化工学院,重庆400715

出　　处：《西南师范大学学报（自然科学版）》2013年第11期32-39,共8页Journal of Southwest China Normal University(Natural Science Edition)

基　　金：西南林业大学科研基金面上资助项目(111130)

摘　　要：运用量子化学从头算(MP2)的方法,在6-311++G(d,p),6-311++G(2df,2p),6-311++G(3df,3pd),aug-cc-pVDZ,aug-cc-pVTZ 5种基组下对HCHO与HNO二聚体、三聚体中蓝移氢键进行研究.研究表明:这4种复合物中,都有C(N)—H…O蓝移氢键形成,并且C(N)—H键收缩且相关震动频率蓝移超过87 cm-1.电子密度拓扑分析表明:所有复合物存在环键点,是正常氢键.自然键轨道(NBO)分析表明:3个主要原因导致这些蓝移氢键的形成:①分子间超共轭作用比较小,可以忽略;②分子内超共轭作用的减小导致σ*(C—H)和σ*(N—H)占据的减小;③存在一定程度的重杂化.Abstract： Ab initio quantum mechanics method（MP2） is employed to investigate the blue shifting H-bonds in the dimmers and tripolymers of HCHO and HNO with the 6-311＋＋G（d, p）, 6-311＋＋G（2df, 2p）, 6-311＋＋G（3df, 3pd）, aug-cc-pVDZ, aug-cc-pVTZ basis sets. In the four complexes, C（N）-H…O blue shifting H-bond is formed where C（N）- H bond contracts and the corresponding stretching frequency blue shifts larger than 87 cm-1. The AIM analysis shows that the topological properties of electron density for four complexes both have RCP and usual H-bonds, where the bond critical point is between H（C） and Y. The NBO analysis shows that three main factors lead to the formation of these blue-shifted H-bonds： （a） intermolecular hyperconjugation is very small and can be neglected; （b） decrease of intramolecular hyperconjugation leads to decrease of occupancy in σ＊（C-H） and σ＊（N-H）; and （c） there exists rehybridization .

关 键 词：蓝移氢键 分子间超共轭 分子内超共轭 重杂化 

分 类 号：O641.1[理学—物理化学]