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在DFT-B3LYP及MP2/6-311++G**水平上分别求得CH3SH…HOCl氢键复合物和CH3SH…ClOH卤键复合物势能面上的稳定构型.频率分析表明,与单体HOCl相比,在两种复合物中,Cl(9)—O(7)和H(8)—O(7)键伸缩振动频率发生显著的红移.经MP2/6-311++G**水平计算的含基组重叠误差(BSSE)校正的气相中相互作用能分别为-19.23和-6.85 kJ·mol-1.自然键轨道理论(NBO)分析表明,在CH3SH…ClOH卤键复合物中,引起Cl(9)—O(7)键变长的因素包括2种电荷转移:(i)孤对电子LP[S(1)]1→σ*[Cl(9)—O(7)];(ii)孤对电子LP[S(1)]2→σ*[Cl(9)—O(7)],其中孤对电子LP[S(1)]2→σ*[Cl(9)—O(7)]转移占主要作用,总的结果是使σ*[Cl(10)—O(11)]的自然布居数增加,同时O(7)和Cl(9)原子s成分均增加的杂化重优具有与电荷转移作用相同的“拉长效应”;在CH3SH…HOCl氢键复合物中也存在类似的电荷转移,但是O(7)原子的再杂化效应不同于前者.自然键共振理论(NRT)进行键序分析表明,在氢键复合物和卤键复合物中,H(8)—O(7)和Cl(9)—O(7)键的键序都减小.通过分子中原子理论(AIM)分析了复合物中氢键和卤键的电子密度拓扑性质.
The stable configurations on the potential energy surface of CH3SH ... HOCl hydrogen bond complex and CH3SH ... ClOH halogen bond complex were obtained at DFT-B3LYP and MP2 / 6-311 ++ G ** levels, respectively. The frequency analysis showed that, In the two complexes, the stretching vibrational frequencies of Cl (9) -O (7) and H (8) -O (7) * The calculated gas-phase interaction energies with base-group overlap error (BSSE) correction for the level calculations are -19.23 and -6.85 kJ · mol-1, respectively. NBO analysis of the CH3SH ... ClOH halo bond complex , The factors that cause the Cl (9) -O (7) bond to lengthen include two types of charge transfer: (i) Lone pair of electrons LP [S (1)] 1 → σ * [Cl (9) -O (ii) Lone pair of electrons LP [S (1)] 2 → σ * [Cl (9) -O (7)], ) -O (7)] transfer, the overall result is to increase the natural population of σ * [Cl (10) -O (11) The increased recombination has the same “stretching effect” as the charge transfer effect; similar charge transfer also exists in the CH3SH ... HOCl hydrogen bonding complex, but the recombination effect of the O (7) atoms is different In the former, Natural Bond Resonance Theory (NRT) The sequence analysis showed that the bond order of H (8) -O (7) and Cl (9) -O (7) bonds decreased both in the hydrogen bond complex and the halogen bond complex. ) Analyzed the topological properties of the electronic density of hydrogen and halogen bonds in the complex.