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在CH3SLi+CH3SH势能面上求得锂键和氢键共存型复合物的两种稳定构型.频率分析表明,与单体相比复合物中S(5)—Li(6)键伸缩振动频率发生红移,而C(8)—H(10)键伸缩振动频率发生蓝移.经B3LYP/6-311++G**,MP2/6-311++G**及MP2/AUG-CC-PVDZ水平计算的含基组重叠误差(BSSE)校正的复合物Ⅰ中相互作用能分别为-58.99,-57.87和-62.89kJ·mol-1.采用自然键轨道(NBO)理论,分析了复合物中单体轨道间的电荷转移,电子密度重排及其与相关键键长变化的本质等.采用分子中的原子(AIM)理论分析了复合物中氢键和锂键的电子密度拓扑性质.在极化连续模型(PCM)下,考察了溶剂化效应.结果表明,所考察的水、二甲亚砜、乙醇和乙醚等四种溶剂均使单体间的相互作用能增大,且溶剂对复合物中的锂键结构及其振动频率具有显著的影响,而对复合物中的氢键的振动频率影响不大.
Two stable configurations of lithium-coexistent and lithium-coexistent complexes were obtained on the CH3SLi + CH3SH potential surface. The frequency analysis showed that the stretching vibration frequency of S (5) -Li (6) And the blue-shift of the stretching frequency of C (8) -H (10) bond occurs by B3LYP / 6-311 ++ G **, MP2 / 6-311 ++ G ** and MP2 / AUG-CC -PVDZ, the interaction energies of complex Ⅰ with base-group overlap error (BSSE) were -58.99, -57.87 and -62.89kJ · mol-1, respectively. Using the theory of natural bond orbital (NBO) Charge transfer, electron density rearrangement and the nature of its bond length changes with the orbitals of the compounds.In this paper, the atomic density (AIM) theory of the molecules was used to analyze the topological properties of the hydrogen bond and the lithium bond in the complex Under the polarization continuous model (PCM), the solvation effect was investigated.The results showed that the four solvents such as water, dimethylsulfoxide, ethanol and ether all increased the interaction between monomers and The solvent has a significant effect on the lithium bond structure and its vibration frequency in the complex, but has little effect on the vibration frequency of the hydrogen bond in the complex.