Theoretical Study on Electron Transfer Matrix Element in Oxidation of α ‐ Amino Carbon‐Centered Radical by O2

Abstract

AbstractAs a successive work of our previous paper,1 the electron transfer matrix element (Vrp) in the oxidation of the simplified model molecule of α‐amino carbon‐centered radical by O2 has been investigated with ab initio calculation at the level of UHF/6‐31 + + G*. Based on the optimized geometries of the reactant and the ion‐pair complex obtained previously, the reaction heat and the inner reorganization energy have been obtained by constructing the potential energy curves of reactant and product states considering the solvent effect with the conductor‐like screening model (COSMO). The solvent reorganization energy has been estimated using Lippert‐Mataga relationship. The calculated results show that the value of Vrp, is several times larger than that of RT, which means that the model reaction is an adiabatic one. Theoretical investigation indicates that the solvent effect on the direct electron transfer (ET) process of oxidation of α‐amino carbon‐centered radical by oxygen is remarkable.