A model electronic Hamiltonian to study low-lying electronic states of [Fe(bpy)3]2+ in aqueous solution.

A simple model electronic Hamiltonian to describe the potential energy surfaces of several low-lying d-d states of the Fe(bpy)(3) complex is developed for use in molecular dynamics (MD) simulation studies. On the basis of a method proposed previously for first-row transition metal ions in aqueous solution, the model Hamiltonian is constructed using density functional theory calculations for the lowest singlet and quintet states. MD simulations are then carried out for the two spin states in aqueous solution in order to examine the performance of the model Hamiltonian. The simulation results indicate that the present model electronic Hamiltonian reasonably describes the potential energy surfaces of the two spin states of the aqueous Fe(bpy)(3) system, while retaining sufficient simplicity for application in simulation studies on excited state dynamics.