The orientation and distance-dependence analysis of the electron transfer reactivity: An electron correlation level investigation of Mn2+ (H2O)(2)/Mn3+(H2O)(2) system

摘要

The structures, properties, and the electron transfer reactivities of Mn2+ (H2O)(2) /Mn3+(H2O)(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 Mn2+ (H2O)(2)/M3+ (H2O)(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. (C) 2000 John Wiley & Sons, Inc. [References: 42]