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在DFT-B3LYP/6-311++G~(**)水平上求得H_2C=S…HCl氢键复合物势能面上的唯一稳定构型,频率分析表明复合物中H—Cl键伸缩振动频率发生显著的红移,红移值为378.3cm?1,与实验值362.3cm~(-1)吻合.经MP2/6-311++G~(**)水平计算的含BSSE校正的相互作用能为-13.59kJ·mol~(-1).自然键轨道理论(NBO)分析表明,引起H—Cl键变长的因素包括3种电荷转移:(1)n_1(S)(sp~(0.31))→σ*(H-Cl);(2)n_2(S)(sp~(40.46))→σ*(H-Cl);(3)σ(H-Cl)→RY*(3)(S)(sp~(3.22)d~(9.32)),其中n2(S)→σ*(H-Cl)的转移占主要作用,总的结果是σ*(H-Cl)的自然布居数增加了50.23me.NBO程序中自然共振理论(NRT)对复合物的键序分析表明H—Cl键被削弱,与红外光谱频率计算分析和电荷转移的结论一致.同时还计算并讨论了H_2C=O…HCl氢键复合物的结构和性质.
The only stable configuration on the potential surface of H_2C = S ... HCl hydrogen bond complex was obtained at the DFT-B3LYP / 6-311 ++ G ~ (**) level. The frequency analysis showed that the H-Cl stretching vibration The redshift value was 378.3 cm -1, which was in good agreement with the experimental value of 362.3 cm -1 .The correlation between BSSE-corrected and MP2 / 6-311 ++ G ~ (**) The action potential energy is -13.59kJ · mol ~ (-1) .Analysis of NBO shows that there are three kinds of charge transfer factors: (1) n_1 (S) (sp ~ (3) σ (H-Cl) → RY * (3)) → σ * (H-Cl) (S ~ (3.22) d ~ (9.32)). The transfer of n2 (S) → σ * (H-Cl) is the main effect. The overall result is the natural population of σ * (H-Cl) The number of bonds increased by 50.23me.Natural resonance theory (NRT) analysis of the bond sequence in the NBO program showed that the H-Cl bond was weakened, which was consistent with the calculation and analysis of infrared spectral frequency and charge transfer.The H_2C = O ... HCl hydrogen bond complex structure and properties.