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Theoretical study of self‐exchange electron‐transfer reactions for the M(H 2 O) \documentclass{article}\pagestyle{empty}\begin{document}$^{2+/3+}_{6}$\end{document} (M = V, Cr, Mn, and Fe) systems
Author(s) -
Zhang Dongju,
Zhuang Bingyou,
Feng Dacheng,
Liu Chengbu
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(2000)78:1<32::aid-qua5>3.0.co;2-j
Subject(s) - chemistry , electron transfer , electron exchange , ionic bonding , ab initio , reaction rate constant , reactivity (psychology) , ionic strength , transition metal , transfer (computing) , activation energy , thermodynamics , ab initio quantum chemistry methods , electron , aqueous solution , metal , atomic physics , ion , kinetics , physics , molecule , quantum mechanics , catalysis , medicine , biochemistry , alternative medicine , organic chemistry , pathology , parallel computing , computer science
Based on an activation model, a available scheme to calculate the rate of the electron‐transfer reaction between transition‐metal complexes in aqueous solution is presented. Ab initio technique is used to determine the electron‐transfer reactivity of the type M(H 2 O) \documentclass{article}\pagestyle{empty}\begin{document}$^{2+/3+}_{6}$\end{document} of transition‐metal complexes at the UMP2/6‐311G level. The activation parameters and activation energies of the electron‐transfer systems are obtained via the activation model. An alternative determining method of the potential energy surface (curve) slope at the crossing point is given in which the inner‐sphere contribution of potential energy surface slope is expressed as the sum of two separate reactants. Theoretical self‐exchange rate constants for M(H 2 O) \documentclass{article}\pagestyle{empty}\begin{document}$^{2+/3+}_{6}$\end{document} (M = V, Cr, Mn, and Fe) systems are obtained at 298 K and zero ionic strength. The calculated results of the activation energy, electronic transmission factor, and electron‐transfer rate are compared with the corresponding quasi‐experimental values as well as those obtained from other methods, and better agreements are found. The present results indicate that the scheme can adequately describe the self‐exchange reactions involved in this study. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 78: 32–41, 2000