Theoretical study of N(C)―H…H―B multi-dihydrogen bonds  

作　　者：KUN Yuan LIU YanZhi Lǔ LingLing 

机构地区：[1]College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741001, China

出　　处：《Chinese Science Bulletin》2009年第7期1182-1189,共8页

基　　金：Support by the Natural Science Education Foundation of Gansu Province (Grant NO. 07-08-12);"QingLan" Talent Engineering Fund of Tianshui Normal University

摘　　要：The optimized geometries, frequencies and interaction energy corrected with basis set superposition error (BSSE) of the multi-dihydrogen bond complexes C4H4NH…BH4.-and CH≡CH…BH4.-have been calculated at both the B3LYP/6-311++G** and the MP2/6-311++G** levels. The calculations were per-formed to study the nature of the N―H…H3―B and C―H…H2―B red shift multi dihydrogen bond in complex C4H4NH…BH-4 and CH≡CH…BH-.4 The BSSE-corrected multi-dihydrogen bond interaction en-ergy of complex I (C4H4NH…BH4-.) and complexⅡ(CH≡CH…BH-.4) is -76.62 and -33.79 kJ/mol (MP2/6- 311++G**), respectively. From the natural bond orbital(NBO)analysis, we detailedly discussed the orbital interactions, electron density transfers, rehybridizations and the essential of the correlative bond length changes in the two complexes. In addition, solvent effect on the geometric structures, vibration frequencies and interaction energy of the monomer and complexes was studied in detail. It is relevant to the relatively dielectric constants (ε).The optimized geometries, frequencies and interaction energy corrected with basis set superposition error （BSSE） of the multi-dihydrogen bond complexes C4H4NH…BH^-4 and CH≡CH…BH^-4 have been calculated at both the B3LYP/6-311＋＋G＊＊ and the MP2/6-311＋＋G＊＊ levels. The calculations were performed to study the nature of the N-H…H3-B and C-H…H2-B red shift multi dihydrogen bond in complex C4H4NH…BH^-4 and CH≡CH…BH^-4 The BSSE-corrected multi-dihydrogen bond interaction energy of complex I （C4H4NH…BH^-4） and complex Ⅱ（CH≡CH…BH^-4） is -76.62 and -33.79 kJ/mol （MP2/6-311＋＋G＊＊）, respectively. From the natural bond orbital （NBO） analysis, we detailedly discussed the orbital interactions, electron density transfers, rehybridizations and the essential of the correlative bond length changes in the two complexes. In addition, solvent effect on the geometric structures, vibration frequencies and interaction energy of the monomer and complexes was studied in detail. It is relevant to the relatively dielectric constants （ε）.

关 键 词：债券 二氢 相互作用能 轨道相互作用 相对介电常数 BSSE 振动频率 B3LYP 

分 类 号：O441.1[理学—电磁学] F832.5[理学—物理]