A theoretical study of photoinduced electron transfer between tetracyanoethylene and arene

Abstract

Ab initio calculations have been performed to investigate the state transition in photoinduced electron transfer reactions between tetracyanoethylene and biphenyl as well as naphthalene. Face-to-face conformations of electron donor–acceptor (EDA) complexes were selected for this purpose. The geometries of the EDA complexes were determined by using the isolated optimized geometries of the donor and the acceptor to search for the maximum stabilization energy along the center-to-center distance. The correction of interaction energies for basis set superposition error was considered by using counterpoise methods. The ground and excited states of the EDA complexes were optimized with complete-active-space self-consistent-field calculations. The theoretical study of the ground state and excited states of the EDA complex in this work reveals that the S1 and S2 states of the EDA complexes are charge–transfer (CT) excited states, and CT absorption which corresponds to the S0→S1 and S0→S2 transitions arise from π−π* excitation. On the basis of an Onsager model, CT absorption in dichloromethane was investigated by considering the solvent reorganization energy. Detailed discussions on the excited state and on the CT absorptions were made.