物理化学学报 >> 1998, Vol. 14 >> Issue (01): 78-83.doi: 10.3866/PKU.WHXB19980115

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几种硫醚化合物的紫外光电子能谱及量子化学研究

孙政, 郑世钧, 孟令鹏, 乔春华, 王殿勋   

  1. 河北师范大学西校区化学系，石家庄 050091|中国科学院化学研究所，北京 100080
  • 收稿日期:1997-04-22 修回日期:1997-09-11 发布日期:1998-01-15
  • 通讯作者: 王殿勋

Hel Photoelectron Spectroscopical and Theoretical Studies of the Electronic Structure and Molecular Obital Character in some Alkyl Thioether Compounds

Sun Zheng, Zheng Shi-Jun, Meng Ling-Peng, Qiao Chun-Hua, Wang Dian-Xun   

  1. Department of Chemistry,Hebei Teachers University,Shijiazhuang 050091|Institute of Chemistry,Chinese Academy of Sciences,Beijing 100080
  • Received:1997-04-22 Revised:1997-09-11 Published:1998-01-15
  • Contact: Wang Dian-Xun

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摘要：

报导了硫酸系列化合物DMS（二甲基硫醚），DpCPS（二对氯苯硫醚），DpTS（二对甲基苯硫醚）气相HeI紫外光电子能谱（UPs），其中DpCPS，DpTS的UPS谱为首次获得．对各体系利用MNDO方法进行了分子构型优化，对优化得到的优势构型实施RHF／6－31G量子化学计算，并利用计算结果对各个分子体系的UPS谱进行了指认，计算结果分析显示：a）S原子的孤对电子在DpCPS和DpTS中起到阻碍形成遍及整个分子体系π轨道的阻断作用，故此不存在遍及整个分子体系的π轨道；b）通过对三体系第一电离能的对比分析表明，第一电离能所激发出的电子主要是受S原子的束缚；c）还得到另一个有意义的结论──各分子体系的第一电离能大小与HOMO中3Pz轨道所占成份成有很好的线性关系．表明体系的第一电离出的电子主要是受S原子的3Pz轨道束缚.

关键词: 硫醚化合物, 紫外光电子能谱, 量子化学计算

Abstract:

 The HeI photoelectron spectra of dimethyl thioether, di-p-chlorphenyl thioether and di-p-tolyl thioether have been studied. To assign these spectra MNDO optimization and RHF/6-31G molecular orbital calculation for the named molecules have also been performed. The results show that: a) The lone-pair electrons of the sulfur atoms can be considered as an obstructor for complete molecular conjugation and so there is no conjugated π bond in the whole molecules; b)The electron which has been ionized by the lowest ionization potentials is bound mainly to the suflur atom, according to the features analysis of the lowest ionization potentials for the named system; c)The RHF/6-31G calculation results show that the lowest ionization potentials of the named compound are directly proptional to the composition of 3Pz of sulfur atom in the HOMO.

Key words: Alkyl thioether, Hel photoelectron spectroscopy, Quantum chemistry calculation