Acta Phys. -Chim. Sin. ›› 2012, Vol. 28 ›› Issue (11): 2574-2580.doi: 10.3866/PKU.WHXB201207302

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

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.

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