Determining Excitation-Energy Transfer Times and Mechanisms from Stochastic Time-Dependent Density Functional Theory

Abstract

We developed an approach for calculating excitation-energy transfer times in supermolecular arrangements based on stochastic time-dependent density functional theory (STDDFT). The combination of real-time propagation and the stochastic Schrödinger equation with a Kohn-Sham Hamiltonian allows for simulating how an excitation spreads through an assembly of molecular systems. The influence that approximations, such as the dipole-dipole coupling approximation of Förster theory, have on energy-transfer times can be checked explicitly. As a first application of our approach we investigate a light-harvesting-inspired model ring system, calculating the time it takes for an excitation to travel from one side of the ring to the opposite side under ideal and perturbed conditions. Among other things we find that completely removing a molecule from the ring may inhibit energy transfer less than having an energetically detuned molecule in the ring. In addition, Förster's dipole coupling approximation may noticeably overestimate excitation-energy transfer efficiency.