Computational Study of Bridge-Assisted Intervalence Electron Transfer

被引：45

作者：

Ding, Feizhi ^{[1
]}

Wang, Haobin ^{[1
]}

Wu, Qin ^{[2
]}

Van Voorhis, Troy ^{[2
]}

Chen, Shaowei ^{[3
]}

Konopelski, Joseph P. ^{[3
]}

机构：

[1] New Mexico State Univ, Dept Chem & Biochem, Las Cruces, NM 88003 USA

[2] MIT, Dept Chem, Cambridge, MA 02139 USA

[3] Univ Calif Santa Cruz, Dept Chem & Biochem, Santa Cruz, CA 95064 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 19期

基金：

美国国家科学基金会;

关键词：

MIXED-VALENCE; STRUCTURAL-PROPERTIES; COMPLEXES; SYSTEMS; COMMUNICATION; FERROCENYL; REDOX; ENERGY; STATE;

D O I：

10.1021/jp912049p

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Intervalence electron transfer reactions were studied computationally by means of density functional theory and constrained density functional theory (CDFT). Two ferrocene moieties, connected via various bridge structures, were used as model mixed-valence compounds in the computational investigation. Features of the frontier orbitals were analyzed to offer a qualitative account of the intervalence characteristics of the model complexes. The effective electronic coupling between the donor and acceptor sites was calculated using the CDFT method, which provided a quantitative measure of the intervalence electronic communication. The relationship between the bridge linkage and the effectiveness of intervalence transfer was discussed on the basis of the theoretical results and compared to experimental data available in the literature.

引用

页码：6039 / 6046

页数：8

共 53 条

[21] ELECTRIC-FIELD INDUCED INTRAMOLECULAR ELECTRON-TRANSFER IN SPIRO PI-ELECTRON SYSTEMS AND THEIR SUITABILITY AS MOLECULAR ELECTRONIC DEVICES - A THEORETICAL-STUDY
FARAZDEL, A
DUPUIS, M
CLEMENTI, E
AVIRAM, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (11) : 4206 - 4214
[22] The redox behaviour of ferrocene molecules .12. The redox behaviour of some bis-ferrocenyl compounds: Crystal and molecular structures of diferrocenylmethane and diferrocenylmethanol
Ferguson, G
Glidewell, C
Opromolla, G
Zakaria, CM
Zanello, P
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 517 (1-2) : 183 - 190
[23] SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .23. A POLARIZATION-TYPE BASIS SET FOR 2ND-ROW ELEMENTS
FRANCL, MM
PIETRO, WJ
HEHRE, WJ
BINKLEY, JS
GORDON, MS
DEFREES, DJ
POPLE, JA
[J]. JOURNAL OF CHEMICAL PHYSICS, 1982, 77 (07) : 3654 - 3665
[24] Frisch M. J., 2004, GAUSSIAN 03
[25] Excited-state distortions and electron delocalization in mixed-valence dimers: Vibronic analysis of the near-IR absorption and resonance Raman profiles of [Fe-2(OH)(3)(tmtacn)(2)](2+)
Gamelin, DR
Bominaar, EL
Mathoniere, C
Kirk, ML
Wieghardt, K
Girerd, JJ
Solomon, EI
[J]. INORGANIC CHEMISTRY, 1996, 35 (15) : 4323 - 4335
[26] HAY PJ, 1985, J CHEM PHYS, V82, P299, DOI [10.1063/1.448800, 10.1063/1.448799]
[27] DISTANCE DEPENDENCE OF ELECTRON-TRANSFER RATES
HUSH, NS
[J]. COORDINATION CHEMISTRY REVIEWS, 1985, 64 (MAY) : 135 - 157
[28] COSMO - A NEW APPROACH TO DIELECTRIC SCREENING IN SOLVENTS WITH EXPLICIT EXPRESSIONS FOR THE SCREENING ENERGY AND ITS GRADIENT
KLAMT, A
SCHUURMANN, G
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (05): : 799 - 805
[29] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY
LEE, CT
YANG, WT
PARR, RG
[J]. PHYSICAL REVIEW B, 1988, 37 (02): : 785 - 789
[30] Electrochemical studies of bi- and polymetallic complexes featuring acetylide based bridging ligands
Low, PJ
Roberts, RL
Cordiner, RL
Hartl, F
[J]. JOURNAL OF SOLID STATE ELECTROCHEMISTRY, 2005, 9 (11) : 717 - 731

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