SLOPES OF THE ENERGY SURFACE OF TRANSITION-METAL IONS IN SOLUTION - A MOLECULAR-ORBITAL CALCULATION

Application of the semiempirical quantum-chemical INDO/2-MO method in computing the slopes of the energy surface of various ions participating in electron-transfer reactions in solution is presented in this paper. The values of slopes obtained from INDO/2-MO agree with those obtained from the classical improved-average-dipole-orientation (IADO) method. Theoretical results of electronic-transmission coefficients of electron-transfer reactions obtained using values of slopes from INDO/2-MO as well as IADO methods are found in close agreement with those obtained from experimental values of rate constants. The values of transmission coefficient are found to be less than unity and these indicate the non-adiabatic nature of electron-transfer reactions involving the transition metal ions studied in this work. © 1990.