(Digital Presentation) Study of the Intervalence Charge Transfer in a 18NaCl+Na₃SmF₆ Model System By Quantum Chemical Methods

Abstract

The frontier orbital method showed a high informativity for the study of electron transfer in the model system 18NaCl+Na3SmF6. Structures having a high probability of electron transfer from the cathode to the samarium complex were observed when varying the transition state parameters. The influence of the full-symmetric oscillations Sm-F bonds and the boundary ion shift on the activation barrier, the frontier molecular orbitals energy and the delocalization character of the lowest unoccupied molecular orbital wave function in the samarium-containing model systems was systematically studied. This analysis allowed to identify the most probable structures of the transition state for the electron transfer process. The application of the method of frontier orbitals made it possible to determine the structure of the transition state of the complex SmF6 3- near the electrode surface with a small costs of machine time, using an agreement of the calculated and experimental values for the activation energy of electron transfer.