高等学校化学学报

高等学校化学学报

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HCN(HNC)与NH3, H2O和HF分子间相互作用的理论研究

汪朝旭, 张敬畅, 曹维良   

  1. 北京化工大学现代催化研究所, 化工资源有效利用国家重点实验室, 北京 100029
  • 收稿日期:2006-03-23 修回日期:1900-01-01 出版日期:2007-02-10 发布日期:2007-02-10
  • 通讯作者: 曹维良

Theoretical Study on Intermolecular Interactions BetweenHCN(HNC) and NH3, H2O, HF

WANG Zhao-Xu, ZHANG Jing-Chang, CAO Wei-liang   

  1. Institute of Modern Catalysis, State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2006-03-23 Revised:1900-01-01 Online:2007-02-10 Published:2007-02-10
  • Contact: CAO Wei-liang

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摘要： 在MP2/aug-cc-pVTZ水平上, 对HCN(HNC)与NH3, H2O和HF分子间可能存在的氢键型复合物进行了全自由度能量梯度优化, 通过在相同水平上的频率验证分析发现了稳定的分子间相互作用形式是HCN(HNC)作为质子供体或作为质子受体形成的复合物. 基组重叠误差对总相互作用能的影响均小于3.34 kJ/mol. 通过自然键轨道(NBO)分析, 研究了单体和复合物中的原子电荷和电荷转移对分子间相互作用的影响. 对称性匹配微扰理论(SAPT, Symmetry Adapted Perturbation Theory)能量分解结果表明, 在分子间相互作用中, 静电作用与诱导作用占主导地位, 而诱导作用与复合物的电荷转移之间具有良好的正相关性.

关键词: HCN(HNC), 分子间相互作用, 基组重叠误差, 自然键轨道, 对称性匹配微扰理论

Abstract: Ab initio molecular orbital calculations including MP2 correlation energy was employed to optimize the geometries of the hydrogen-bonded complexes formed by HCN(HNC) with NH3, H2O and HF, respectively at aug-cc-pVTZ level. It was found that there were two kinds of stable complexes bonded by intermolecular hydrogen bonds: HCN(HNC) as the proton donor and as the proton acceptor. The effect of basis set superposition error on the total interaction energy is smaller than 3.34 kJ/mol. Natural bond orbital (NBO) analysis was performed to analyze the atomic charges and charges transfer in the monomers and complexes. The results of the decomposition of interaction energy according to SAPT2 show that the electrostatic and induction forces dominate the intermolecular interaction, and there is a good correlation between induction forces and charges transfer.

Key words: HCN(HNC), Intermolecular interaction, Basis set superposition error(BSSE), Natural bond orbital(NBO), Symmetry adapted perturbation theory(SAPT)

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