Premium
Nonempirical ab initio studies on inner‐sphere reorganization energies of M 2+ (H 2 O) 6 /M 3+ (H 2 O) 6 redox couples at valence basis level
Author(s) -
Bu Yuxiang,
Ding Yangjun,
He Faxin,
Jiang Lifu,
Song Xinyu
Publication year - 1997
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(1997)61:1<117::aid-qua14>3.0.co;2-b
Subject(s) - inner sphere electron transfer , chemistry , valence (chemistry) , coordination sphere , electron transfer , ab initio , ion , redox , molecular orbital , atomic physics , computational chemistry , molecular physics , molecule , physics , inorganic chemistry , organic chemistry
On the basis of the basic feature of the electron transfer reactions, a new theoretical scheme and application of a nonempirical ab initio method in computing the inner‐sphere reorganization energies (RE) of hydrated ions in electron transfer processes in solution are presented at valence STO basis (VSTO) level. The potential energy surfaces and the various molecular structural parameters for transition metal complexes are obtained using nonempirical molecular orbital (MO) calculations, and the results agree very well with experimentally observed ones from vibrational spectroscopic data. The results of inner‐sphere REs obtained from these calculations via this new scheme give a good agreement with photoemission experimental findings and those from the improved self‐exchange model proposed early for M 2+ (H 2 O) 6 /M 3+ (H 2 O) 6 (M = V, Cr, Mn, Fe, and Co) redox couple systems and are better than those from semiempirical INDO/II MO method and other classical methods. Further, the observed agreement of the optimized structural data and the results of inner‐sphere REs of complexes with experimental findings confirms the following: (1) the validity of nonempirical MO calculation method to get accurate structural parameters and inner‐sphere RE for the redox systems for which reliable vibrational spectroscopic data are not available, (2) the validity of the improved self‐exchange model proposed early for inner‐sphere RE, and (3) the reasonableness of some approximations adopted in this study. © 1997 John Wiley & Sons, Inc.