物理化学学报 >> 2010, Vol. 26 >> Issue (09): 2523-2528.doi: 10.3866/PKU.WHXB20100924

量子化学及计算化学 上一篇    下一篇

饱和烷烃分子CnH2n+2(n=4-6)的电子动量光谱

杨则金2, 郭云东1, 朱正和2, 杨向东2   

  1. 1. 内江师范学院物理与电子信息工程学院, 四川内江641112;
    2. 四川大学原子与分子物理研究所, 成都610065
  • 收稿日期:2010-04-10 修回日期:2010-07-16 发布日期:2010-09-02
  • 通讯作者: 郭云东 E-mail:g308yd@126.com
  • 基金资助:

    国家自然科学基金(10676025,10574096),国家留学基金委员会(CSC)和四川省青年科技基金(09ZQ026-049)资助项目

ElectronMomentumSpectroscopy for Saturated Alkanes CnH2n+2(n=4-6)

YANG Ze-Jin2, GUO Yun-Dong1, ZHU Zheng-He2, YANG Xiang-Dong2   

  1. 1. School of Physics and Electronic Information Engineering, Neijiang Normal University, Neijiang 641112, Sichuan Province, P. R. China;
    2. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, P. R. China
  • Received:2010-04-10 Revised:2010-07-16 Published:2010-09-02
  • Contact: GUO Yun-Dong E-mail:g308yd@126.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (10676025, 10574096), China Scholarship Council (CSC), and Science-Technology Foundation for Young Scientist of Sichuan Province, China (09ZQ026-049).

摘要:

使用B3LYP/TZVP//B3LYP/aug-cc-pVTZ 方法系统研究了饱和烷烃分子CnH2n+2(n=4-6)的轨道电子动量光谱, 比较了同分异构体CnH2n+2(n=4-6)对轨道动量分布的影响. 结合二维空间分析方法对电子在坐标空间中的密度分布进行了系统的研究. 计算结果表明,最内价壳层电荷分布主要由s 电子贡献, 第二近邻芯价壳层则主要由p电子贡献,而其余的价壳层则为sp 杂化. 最内价轨道表现出最大的谱线强度并且远大于其它轨道的谱线强度,而且正烷烃的谱线强度要大于异烷烃等同分异构体的谱线强度, 表现出了明显的与甲基移动的个数有关的性质.

关键词: 电子动量光谱, 二维空间分析, 饱和烷烃

Abstract:

Orbital electron momentum spectroscopies for saturated alkanes CnH2n+2(n=4-6) were systematically studied using the B3LYP/TZVP//B3LYP/aug-cc-pVTZ model. The effect of saturated alkanes CnH2n+2(n=4-6) isomers on orbital momentum distributions was analyzed. Electronic density distributions of coordinate space were systematically investigated by dual space analysis. The results indicate that the innermost valence orbitals are s-dominated whereas the next innermost valence orbitals exhibit p-dominant orbital profiles. The other valence orbitals are sp-mixed because of strong chemical bonding. The relative intensity of innermost valence orbitals is far larger than that of other orbitals. Furthermore, the relative intensity of n-alkane is larger than that of iso-alkane, which indicates that there is an obvious correlation between the relative intensity and the number ofmigratedmethyls.

Key words: Electron momentumspectroscopy, Dual space analysis, Saturated alkane

MSC2000: 

  • O644