物理化学学报 >> 2012, Vol. 28 >> Issue (11): 2574-2580.doi: 10.3866/PKU.WHXB201207302

理论与计算化学 上一篇    下一篇

非对称笼间电子迁移异构体与电场诱导电子迁移

王银锋1, 黄俭根1, 周光培1, 李志儒2   

  1. 1 井冈山大学化学化工学院, 井冈山大学应用化学研究所, 江西省配位化学重点实验室,江西 吉安 343009;
    2 吉林大学理论化学研究所, 长春 130023
  • 收稿日期:2012-06-08 修回日期:2012-07-30 发布日期:2012-10-17
  • 通讯作者: 王银锋, 李志儒 E-mail:cyclont@yeah.net; lzr@jlu.edu.cn
  • 基金资助:

    江西省科技厅自然科学基金(20114BAB213007); 江西省教育厅自然科学基金(GJJ12486); 国家自然科学基金(21173098); 井冈山大学博士启动基金(JZ10045)及吉林大学理论计算化学国家重点实验室开放课题基金资助项目

Asymmetrical Inter-Cage Electron Transfer Electromers and Their Transfer Characteristics Under Electric Fields

WANG Yin-Feng1, HUANG Jian-Gen1, ZHOU Guang-Pei1, LI Zhi-Ru2   

  1. 1 School of Chemistry and Chemical Engineering, Institute of Applied Chemistry, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji’an 343009, Jiangxi Province, P. R. China;
    2 State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China
  • Received:2012-06-08 Revised:2012-07-30 Published:2012-10-17
  • Supported by:

    The project was supported by the Science and Technology Project of Jiangxi Provincial Department of Science & Technology, China (20114BAB213007), Science and Technology Project of Jiangxi Provincial Department of Education (GJJ12486), National Natural Science Foundation of China (21173098), DrStart-up Fund Research of Jinggangshan University (JZ10045), China, and Foundation of State Key Laboratory of Theoretical and Computational Chemistry of Jilin University, China.

摘要:

基于密度泛函理论研究了非对称双笼型单分子溶剂化电子e-@C24F22(NH)2C20F18(1、2 和3), 进一步展示了我们提出的一种新型电子异构体——(非对称型的)笼间电子迁移异构体. 1、2 和3 具有显著不同的偶极矩. 由于都存在两个氧化还原中心, 它们属于一种非金属型的新型Robin-Day II-III 分子. 对于1 和3, 额外电子分别定域在C24F22和C20F18笼里(Robin-Day II); 对于2, 额外电子则离域于两个非对称的笼中(Robin-Day III). 值得注意的是, 在y 轴方向上外加-0.0004和-0.0008 a.u.的临界电场(Ec)时可分别使1 的额外电子从C24F22笼中部分和全部地迁移到C20F18笼中, 即实现从1 到2 再到3 的转化; 当Ec为0.0004 a.u.时, 3 的额外电子从C20F18笼中全部迁移到了C24F22笼中, 即3 未经过2 直接转化成了1.

关键词: 电场诱导, Robin-Day分子, 单分子溶剂化电子, 电子异构体, 不对称笼间电子迁移

Abstract:

The asymmetrical, double-cage-shaped, single molecular solvated electron compounds e-@C24F22(NH)2C20F18 (1, 2, and 3) were investigated based on density functional theory (DFT). This work revealed a novel species of electromer consisting of asymmetrical inter-cage electron-transfer isomers. These inter-cage electron-transfer isomers belong to a new form of Robin-Day class II-III molecules. 1 and 3 are Robin-Day class II, with the excess electron inside the C24F22 and C20F18 cages respectively, while 2 is class III with the excess electron inside both cages. These electromers were found to exhibit significantly different dipole moments. The application of external electric fields of -0.0004 or -0.0008 a.u. in the y-axis direction of 1 resulted in either partial or whole transfer of the excess electron from C24F22 to C20F18, allowing conversion from 1 to 2 or 3. An Ec value of 0.0004 a.u. was determined, indicating that the excess electron can wholly transfer from the C20F18 cage to C24F22, resulting in conversion from 3 to 1 without going through 2.

Key words: Electric field inducement, Robin-Day molecule, Single molecular solvated electron, Electromer, Asymmetrical inter-cage electron transfer

MSC2000: 

  • O641