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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (11): 2031-2033. 上一篇    

研究论文

两种影响生态环境的亚硝基取代烷烃的电子结构

孙政;郑世钧;王殿勋   

  1. 中国科学院化学研究所动态及稳态结构国家重点实验室;河北师范大学化学系. 石家庄(050016)
  • 发布日期:2001-11-15

Photoelectron spectroscopic (PES) and theoretical studies on two alkyl nitrites that affect the eco-environment

Sun Zheng;Zheng Shijun;Wang Dianxun   

  1. Hebei Teachers Univ, Dept Chem.Shijiazhuang(050016)
  • Published:2001-11-15

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410

被引次数

3 | 1

采用紫外光电子能谱实验(PES)和量子化学方法对两种影响生态环境的亚硝基取代烷烃RONO[R=(CH3)2CH,(CH3)3CO]的电子结构进行了分析和讨论。实验得到两种化合物的第一电离能分别为10.37eV和10.12eV,结合从头算自洽场分子轨道(abinitioSCFMO)计算和外壳层格林函数法(OVGF)计算对PES进行了分析和指认。研究表明化合物中取代基效应对电离能存在明显的影响；外层格林函数法计算得到电离能与实验吻合很好；同时发现在外层格林函数计算结果中由于考虑相关能，得到的分子轨道存在能级顺序的交错。实验和理论计算结果进一步证实亚硝基取代烷烃是产生烷基氧自由基(RO^.)的很好的源物种，这为深入研究由它们产生的对环境破坏有着重要影响的相应自由基奠定了基础。

关键词: 亚硝基, 烷烃P, 从头计算法, 电子结构, 自洽场

The photoelectron spectroscopy (PES) of iso-propyl nitrite (CH3) 2CHONO and tert -butyl nitrite (CH3)3CONO are reported. By combining the PES measurements with theoretical calculation on the compounds, we conclude that the first vertical ionization potential for the two compounds are 10.37 and 10.12 eV, respectively. An unmistakable substituent effect on the ionization potential was observed. Comparison of different calculations shows that the outer valence Green's function (OVGF) method gives quite good results in ionization potentials calculations. It is also pointed out that alkyl nitrites are good source for obtaining RO^. radicals based on the experimental and theoretical analysis.

Key words: NITROSO GROUPS, ALKANE P, AB INITIO CALCULATION, ELECTRONIC STRUCTURE, SELF-CONSISTENT FIELD

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