化学学报 ›› 2004, Vol. 62 ›› Issue (4): 433-435. 上一篇    下一篇

研究简报

BrCl紫外光电子能谱实验及理论研究

乔志敏1,2, 孙巧1,2, 孙树涛1,2, 王殿勋1   

  1. 1. 中国科学院化学研究所, 动态与稳态结构国家重点实验室, 北京, 100080;
    2. 中国科学院研究生院, 北京, 100039
  • 收稿日期:2003-05-07 修回日期:2003-10-16 出版日期:2004-02-28 发布日期:2014-01-26
  • 通讯作者: 王殿勋,E-mail:wangdx@infoc3.icas.ac.cn E-mail:wangdx@infoc3.icas.ac.cn
  • 基金资助:
    国家自然科学基金(Nos.29973051,20073052和20073042)资助项目.

Photoelectron Spectroscopy (PES) and Theoretical Studies on Bromine Monochloride

QIAO Zhi-Min1,2, SUN-Qiao1,2, SUN Shu-Tao1,2, WANG Dian-Xun1   

  1. 1. State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080;
    2. Graduate School of Chinese Academy of Sciences, Beijing 100039
  • Received:2003-05-07 Revised:2003-10-16 Online:2004-02-28 Published:2014-01-26

采用紫外光电子能谱研究了影响大气臭氧浓度的重要卤素互化物一氯化溴的精细电离能谱.实验得到BrCl的第一绝热电离能和垂直电离能分别为10.95 eV和11.00 eV. BrCl的最高占据轨道6π电离产生了明显的旋轨分裂谱带.这对旋轨分裂谱带分别清晰地显示出4个振动精细结构峰.频率分析显示BrCl分子最高占据轨道为弱反键性质.比较了HF方法和外壳层格林函数方法(OVGF)对电离能的计算结果,并对实验值进行了分析比较及指认.采用实验构型OVGF方法给出的电离能结果无论在低电离能区还是在高电离能区都和实验值一致,特别是第一垂直电离能10.988 eV与实验值11.00 eV非常好地吻合.

关键词: 光电子能谱, 一氯化溴, 电离能, OVGF

Bromine monochloride has been thought to play an important role in surface ozone depletion at polar sunrise recently. The photoelectron spectroscopy (PES) of BrCl is reported. Research shows that the first adiabatic and vertical ionization potential of bromine monochloride are 10.95 eV and 11 00 eV, respectively. The removal of an electron from the highest occupied orbital (HOMO) of bromine monochloride leads to obvious spin orbit coupling peaks which exhibit fine vibrational structure. The analysis of vibrational frequencies shows that the HOMO has a slightly antibonding character. Comparison of different calculations indicates that the Outer Valence Green's Function (OVGF) method gives extremely good results in the calculation of ionization potential, which is in excellent accordance with the experimental values, especially the first vertical ionization potential (10 988 eV).

Key words: photoelectron spectroscopy, bromine monochloride, ionization potential, outer valence green’s function(OVGF)