物理化学学报 >> 2008, Vol. 24 >> Issue (05): 861-867.doi: 10.3866/PKU.WHXB20080522

研究论文 上一篇    下一篇

气相中开壳型(CH3)2S(O)…HOO红移氢键复合物的结构与性质

袁焜; 刘艳芝; 吕玲玲   

  1. 天水师范学院生命科学与化学学院, 甘肃 天水 741001
  • 收稿日期:2007-12-07 修回日期:2008-01-07 发布日期:2008-05-05
  • 通讯作者: 袁焜 E-mail:yuankun@mail.tsnc.edu.cn

Red Shift Hydrogen Bond of Open-Shell (CH3)2S(O)…HOO Complexes in Gas Phase: Structures and Properties

YUAN Kun; LIU Yan-Zhi; LV Ling-Ling   

  1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741001, Gansu Province, P. R. China
  • Received:2007-12-07 Revised:2008-01-07 Published:2008-05-05
  • Contact: YUAN Kun E-mail:yuankun@mail.tsnc.edu.cn

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摘要： 在DFT-B3LYP/6-311++G**水平上分别求得(CH3)2S…HOO和(CH3)2O…HOO开壳型氢键复合物势能面上的稳定构型. 频率分析表明, 与单体HOO自由基相比, 复合物中H10-O11键伸缩振动频率发生显著的红移, 红移值分别为424.21和374.22 cm-1. 在MP2/6-311++G**水平计算得到, 含基组重叠误差(BSSE)校正和零点振动能(ZPVE)校正的相互作用能分别为-24.68和-31.01 kJ·mol-1. 自然键轨道(NBO)理论分析表明, 在(CH3)2S…HOO复合物中, 引起H10-O11键变长的因素包括两种电荷转移: (1) LP(S1)1→σ*(H10-O11); (2) LP(S1)2→σ*(H10-O11), 其中LP(S1)2→σ*(H10-O11)占主要作用, 总的结果是使σ*(H10-O11)的自然布居数增加了37.27 me; 在(CH3)2O…HOO中也有相似的电荷转移的超共轭作用. AIM理论分析表明, S1…H10间和O1…H10间都存在键鞍点, ▽2ρ(r)分别为0.06196和0.03745, 说明这种相互作用介于共价键和离子键之间, 偏于静电作用.

关键词: 二甲基硫, 氢过氧自由基, 氢键复合物, 自然键轨道理论, 分子中原子理论

Abstract: The optimized stable (CH3)2S…HOO and (CH3)2O…HOO hydrogen bond complexes were found on the potential energy surface at B3LYP/6-311++G** level. The obvious red shifts of the H10-O11 stretch vibration in the two hydrogen bond complexes were obtained by frequency analysis, and the red shift values were 424.21 and 374.22 cm-1, respectively. The hydrogen bond of S1(O1)…H10 interaction energy were -24.68 and 31.01 kJ·mol-1, which was calculated with basis set superposition error (BSSE) and zero point vibrational energy (ZPVE) correction at MP2 level. Natural bond orbit (NBO) theory analysis showed that two kinds of charge transfer exist in (CH3)2S…HOO hydrogen bond complex: (1) LP(S1)1→σ*(H10-O11); (2) LP(S1)2→σ*(H10-O11), and the natural population of the σ*(H10-O11) increased by 37.27 me. Analogous charge transfers existed in (CH3)2O…HOO hydrogen bond complex. Bond order analysis with nature resonance theory (NRT) showed that H10-O11 bond order decreased both in (CH3)2S…HOO and (CH3)2O…HOO hydrogen bond complexes. This agreed with the charge transfer discussion and frequency analysis. The topological properties of the hydrogen bond structures were also investigated by the atom-in-molecules (AIM) theory, and the results showed that there exist bond critical points between S1(O1) and H10.

Key words: (CH3)2S, HOO, Hydrogen bond complexes, NBO theory, AIM theory