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在DFT-B3LYP/6-311++G**水平上分别求得O3…ClOH氯键复合物和O3…HOCl氢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,分别在两种复合物中,Cl4-O5和H6-O5键伸缩振动频率发生红移,红移值分别为5.70和76.44 cm-1.经MP2/6-311++G**水平计算的含BSSE和零点振动能校正的气相中相互作用能分别为-2.102和-4.920 kJ.mol-1.NBO分析表明,在O3…ClOH氯键复合物中,引起Cl4-O5键变长的因素包括2种电荷转移:(1)LP(O1)1→σ*(Cl4-O5);(2)LP(O1)2→σ*(Cl4-O5),其中LP(O1)2→σ*(Cl4-O5)转移占主要作用,总的结果是使σ*(Cl10-O11)的自然布居数增加了14.44 me;在O3…HOCl氢键复合物中也存在类似的电荷转移,结果使σ*(H6-O5)的自然布居数增加了18.09 me.NRT理论进行键序分析表明,在氯键复合物和氢键复合物中,Cl4-O5和H6-O5键的键序都减小,与红外光谱频率计算分析和NBO分析的结论一致.AIM理论分析表明,分别在两种复合物中,O1…Cl4间和O1…H6间都存在键鞍点,而且O1…Cl4和O1…H6的ρ(r)都较小,分别为0.0111和0.0152 a.u.,说明复合物中的氯键和氢键相互作用较弱.另外,O1…Cl4氯键和O1…H6氢键的Lapla-cian量2ρ(r)分别为0.0479和0.0641 a.u.,都是较小的正值,说明这两种相互作用都以静电作用为主.
The stable configuration on the potential surface of O3 ... ClOH hydrogen bond complex and O3 ... HOCl hydrogen bond complex was obtained at the level of DFT-B3LYP / 6-311 ++ G **, respectively. The frequency analysis showed that the HOCl phase In each of the two complexes, the stretching vibrational frequencies of Cl4-O5 and H6-O5 were red shifted by 5.70 and 76.44 cm-1, respectively. The MP2 / 6-311 ++ G ** level The interaction energies in the gas phase with BSSE and zero-point vibrational energy correction are -2.102 and -4.920 kJ · mol -1, respectively. The analysis of the NBO shows that in the O 3 ClOH chloride bond complex, the factors that cause the Cl 4 -O 5 bond to lengthen Including two kinds of charge transfer: (1) LP (O1) 1 → σ * (Cl4-O5); (2) LP (O1) 2 → σ * (Cl4-O5) Cl4-O5) transfer, the overall result is to increase the natural population of σ * (Cl10-O11) by 14.44 me. Similar charge transfer also exists in the O3 ... HOC1 hydrogen bond complex. As a result, σ * (H6-O5) natural population increased by 18.09 me.NRT theory of key sequence analysis showed that the chlorine bond complex and hydrogen bond complexes, Cl4-O5 and H6-O5 bond order are reduced , Which is consistent with the results of infrared spectrum frequency analysis and NBO analysis.AIM theoretical analysis shows that in the two complexes , O1 ... Cl4 and O1 ... H6, and the ρ (r) of O1 ... Cl4 and O1 ... H6 are smaller, which are 0.0111 and 0.0152 au, respectively, indicating that the chlorine bond and the hydrogen bond in the complex interact with each other In addition, the Laplacian quantities 2ρ (r) of O1 ... Cl4 and O1 ... H6 hydrogen bonds are 0.0479 and 0.0641 au, respectively, which are all smaller positive values, indicating that both the interactions are electrostatic Role-based.