Chem. J. Chinese Universities ›› 2009, Vol. 30 ›› Issue (10): 2049.

• Articles • Previous Articles     Next Articles

Structures and Electron Density Topological Properties of the CH3SH…HOO Hydrogen Bond Complexes

LIU Yan-Zhi1*, SHI Xiao-Ning1, LI Zhi-Feng1, TANG Hui-An1, YUAN Kun1, ZHANG Jun-Yan2   

  1. 1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741001, China;
    2. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
  • Received:2008-09-16 Online:2009-10-10 Published:2009-10-10
  • Contact: LIU Yan-Zhi. E-mail: lyanzhi003@163.com
  • Supported by:

    天水师范学院“青蓝”人才工程基金(批准号: 09004)和甘肃省教育厅研究生导师科研基金(批准号: 070812)资助.

Abstract:

The four optimized stable CH3SH…HOO hydrogen bond complexes(14) were found on the potential energy surface at B3LYP/6-311++G** level. The calculated results showed that the complexes 1 and 2 use the H7 atom of HOO as proton donor and the S5 atom of CH3SH as acceptor, and the obvious red shifts of the H7—O8 stretch vibration in the two hydrogen bond complexes were obtained by frequency analysis, and the red shift values were 330.1 and 320.4 cm-1, respectively. As for complexes 3 and 4, they use the H6 atom of CH3SH as proton donor and the terminal O9 of HOO as acceptor. The hydrogen bond interaction energies in the four complexes were -20.81, -20.10, -4.46 and -4.52 kJ/mol, which were calculated with basis set superposition error(BSSE) correction at MP2 level. Natural bond orbital(NBO) theory analysis showed that two kinds of charge transfer exist in CH3SH…HOO hydrogen bond complexes 1 and 2: (1) lone pair n1(S5)→σ*(H7—O8), (2) lone pair n2(S5)→σ*(H7—O8). Analogous charge transfers existed in complexes 3 and 4, but the orbital interactions are weaker. The topological properties of the hydrogen bond structures were also investigated by the atom-in-molecules(AIM) theory, and the results showed that there exist hydrogen bond critical points in four complexes.

Key words: CH3SH; HOO; H-bond complex; Natrual bond orbital theory; Electron density topological pro-perty

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