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The orientation and distance‐dependence analysis of the electron transfer reactivity: An electron correlation level investigation of Mn 2+ (H 2 O) 2 /Mn 3+ (H 2 O) 2 system
Author(s) -
Bu Yuxiang,
Liu Chengbu
Publication year - 2000
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/1096-987x(20001130)21:15<1387::aid-jcc6>3.0.co;2-t
Subject(s) - chemistry , electron , wave function , ab initio , atomic physics , electronic correlation , orientation (vector space) , electron transfer , projection (relational algebra) , coupling (piping) , electronic structure , basis set , molecular physics , computational chemistry , physics , quantum mechanics , density functional theory , geometry , materials science , mathematics , algorithm , organic chemistry , metallurgy
The structures, properties, and the electron transfer reactivities of Mn 2+ (H 2 O) 2 /Mn 3+ (H 2 O) 2 have been investigated in this article at the different levels of theory. The geometrical optimizations that have been made at the UMP2(full)/6‐311+G* level for these two species, the binding characteristics, natural orbital analysis, and the electronic configurations, have been discussed at the UMP2(full)/6‐311+G* optimized geometries. A novel description scheme is presented for the overall electron transfer rate and calibrated by the Mn 2+ (H 2 O) 2 /Mn 3+ (H 2 O) 2 pair. The relevant energy quantities are also calculated at different levels of theory including MP2, MP3, MP4, and QCISD, and corresponding spin‐projection PMP2 and PMP3 with the same basis set (6‐311+G*). In the calculations, all electrons are correlated. The electronic transmission coefficient is calculated using the ab initio potential energy surface slopes and the coupling matrix element determined from the two‐state model and the Slater‐type d‐electron wave functions. The pair distribution function is determined by using a new method presented here. The contact distance dependence and orientation dependence of relevant parameters and the applicability of the presented models are also discussed. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1387–1404, 2000