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在b3lyp/6-311++g**和mp2/6-311++g**水平上研究了CH3SO与HOCl之间的弱相互作用,分别得到了9种和5种稳定复合物S1A～S9A(复合物A)和S4B～S7B及S10B(复合物B),进一步在mp2/6-311++g**水平下,利用自然键轨道理论(NBO)和分子中的原子理论(AIM)对其本质进行了详细讨论,计算了经BSSE矫正的mp2/6-311++g**及ccsd(t)/6-311++g**相互作用能.结果表明,体系中除存在氢键与氯键两种弱相互作用外,还存在新型的氧键(S6)弱相互作用(S…O-F,S…O-Cl,S…O-Br).S1A～S9A及S4B～S7B,S10B的相互作用能分别在-0.4～-41.4kJ·mol-1和-6.9～-35.8kJ·mol-1之间,且其变化规律与ccsd(t)/6-311++g**水平一致.在S6中,主要发生LP1(S8)与σ*.(O5-Cl7)之间的电荷转移,导致O5-Cl7拉长,伸缩振动频率减小,产生红移氧键复合物.不同的是,mp2/6-311++g**水平下的S6B-F,S6B-Br及S7B均为蓝移型复合物.S10B兼有红移和蓝移的“双重”特性.
The weak interaction between CH3SO and HOCl was studied at b3lyp / 6-311 ++ g ** and mp2 / 6-311 ++ g ** levels, and nine stable complexes of S1A to S9A (Complex A) and S4B-S7B and S10B (complex B) were synthesized by using the theory of natural bond orbital theory (NBO) and atomic atom theory (AIM) in the molecule at mp2 / 6-311 ++ g ** Its nature has been discussed in detail, and the interaction energies of mp2 / 6-311 ++ g ** and ccsd (t) / 6-311 ++ g ** corrected by BSSE have been calculated.The results show that in addition to hydrogen bond In addition to the two weak interactions with chlorine bonds, there are also new weak interactions of oxygen bonds (S6) (S ... OF, S ... O-Cl, S ... O-Br) .S1A to S9A and S4B to S7B, The interaction between them can be between -0.4 ~ -41.4kJ · mol-1 and -6.9 ~ -35.8kJ · mol-1, respectively, and its variation is consistent with the level of ccsd (t) / 6-311 ++ g **. In S6, the charge transfer between LP1 (S8) and σ *. (O5-Cl7) occurs mainly, resulting in the elongation of O5-Cl7 and the decrease of stretching vibration frequency, resulting in the red shift oxygen bond complex. S6B-F, S6B-Br, and S7B are blue shifted complexes at mp2 / 6-311 ++ g ** levels, and the “double” feature of both redshift and blue shift for S10B.