The self-exchange of a nonbonding electron via the outer-sphere pathway: reorganizational energy and electronic coupling matrix element for the V(OH2)62+/3+, Ru(OH2)62+/3+, V(OH2)63+/4+, and Ru(OH2)63+/4+ couples

2002 ◽  
pp. 719 ◽  
Author(s):  
François P. Rotzinger
Keyword(s):  
Matrix Element ◽  
Outer Sphere ◽  
The Self ◽  
Electronic Coupling ◽  
Coupling Matrix

Transition Flux Formula for the Electronic Coupling Matrix Element

2015 ◽  
Vol 119 (24) ◽  
pp. 7712-7721 ◽  
Author(s):  
Muhammad A. Hagras ◽  
Alexei A. Stuchebrukhov
Keyword(s):  
Matrix Element ◽  
Electronic Coupling ◽  
Coupling Matrix ◽  
Flux Formula

Theoretical Study of Solvent Effects on the Electronic Coupling Matrix Element in Rigidly Linked Donor-Acceptor Systems

1995 ◽  
Vol 99 (49) ◽  
pp. 17501-17504 ◽  
Author(s):  
Robert J. Cave ◽  
Marshall D. Newton ◽  
Krishna Kumar ◽  
Matthew B. Zimmt
Keyword(s):  
Matrix Element ◽  
Solvent Effects ◽  
Theoretical Study ◽  
Electronic Coupling ◽  
Coupling Matrix ◽  
Donor Acceptor

Semiclassical and quantum-mechanical study of the reaction mechanism for the N2 + N2+ electron transfer system

2003 ◽  
Vol 81 (2) ◽  
pp. 125-132
Author(s):  
Yu-Mei Xing ◽  
Lan Chen ◽  
Chong Zhang ◽  
Zun-Sheng Cai ◽  
Xue-Zhuang Zhao
Keyword(s):  
Electron Transfer ◽  
Matrix Element ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Transmission Factor ◽  
Quantum Mechanical ◽  
Electronic Coupling ◽  
Transfer System ◽  
Coupling Matrix ◽  
Electron Transfer System

Density functional theory (DFT) calculations, including electron correlation, were carried out on the N2 + N2+ electron transfer system. Six geometries of the precursor complex were assumed and their stabilities were calculated and compared. The activation energy, the electronic transmission factor, and the electronic coupling matrix element in the electron transfer process were also calculated. The electronic transmission factor for this system was far less than unity (ca. 0.006~0.09); thus, the electron transfer reaction was considered to be diabatic in nature. Therefore, the electron transfer rate for the selected structures was calculated using semiclassical and quantum-mechanical theories. The calculated values were compared with each other and were in good agreement with the experimental value.Key words: N2 + N2+ electron transfer reaction, semiclassical and quantum-mechanical theories, electronic transmission factor, electronic coupling matrix element, B3LYP.

scholarly journals Direct Determination of the Electron-Phonon Coupling Matrix Element in a Correlated System

2010 ◽  
Vol 105 (25) ◽  
Author(s):  
Huajun Qin ◽  
Junren Shi ◽  
Yanwei Cao ◽  
Kehui Wu ◽  
Jiandi Zhang ◽  
...  
Keyword(s):  
Matrix Element ◽  
Direct Determination ◽  
Phonon Coupling ◽  
Coupling Matrix ◽  
Electron Phonon Coupling

Electron transfer reactions of nickel complexes of 1,4,7-triazacyclodecane

1985 ◽  
Vol 63 (11) ◽  
pp. 2983-2989 ◽  
Author(s):  
M. G. Fairbank ◽  
A. McAuley ◽  
P. R. Norman ◽  
O. Olubuyide
Keyword(s):  
Electron Transfer ◽  
Exchange Rate ◽  
Proton Transfer ◽  
Electrochemical Oxidation ◽  
Rate Constant ◽  
Aqueous Media ◽  
Nickel Complexes ◽  
Outer Sphere ◽  
The Self ◽  
Transfer Reactions

The preparation of [Ni(1,4,7-triazacyciodecane)2]3+, (Ni(10-aneN3)23+) is described. The existing procedure has been modified leading to good yields of the ligand trihydrochloride. The nickel(II) analogue (reported previously) is oxidised in a facile manner, either by Co3+aq in acidic aqueous media or by NO+ in CH3CN. Since the octahedral NiN6, chromophore is retained upon electron transfer, outer sphere reactions both of the Ni(II) and Ni(III) species have been studied. Rates of oxidation by various nickel(III) macrocycles have been measured and details are provided. Electrochemical oxidation of the Ni(II) complex is consistent with E0(Ni(10-aneN3)23+/2+) = 0.997 V (vs. NHE). The data have been used in a Marcus correlation, leading to the self-exchange rate k11 for the couple (Ni(10-aneN3)23+/2+) = (2 ± 1) × 104 M−1 s−1. This value is compared with other data derived using octahedral Ni(II)/Ni(III) centres. The oxidation of the Ni(II) complex by Co(III)aq has been studied in both protonated and deuterated media. There is no evidence for any proton transfer (from the N—H) being coupled to the electron transfer step. The observed rate constant for the reaction of Co3+ with Ni(II)(10-aneN3)22+ (550 M−1 s−1) may be compared with the calculated outer sphere rate (270 M−1 s−1). An estimate of k11 (CoOH2+/+) ~ 3 M−1 s−1 for the CoOH2+/+ exchange is discussed.

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