非对称笼间电子迁移异构体与电场诱导电子迁移

doi:10.3866/PKU.WHXB201207302

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 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

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 E_c 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

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WANG Yin-Feng, HUANG Jian-Gen, ZHOU Guang-Pei, LI Zhi-Ru. Asymmetrical Inter-Cage Electron Transfer Electromers and Their Transfer Characteristics Under Electric Fields[J].Acta Phys. -Chim. Sin., 2012, 28(11): 2574-2580.

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

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