A non-self-consistent range-separated time-dependent density functional approach for large-scale simulations

Abstract

We propose an efficient method for carrying out time-dependent density functional theory (TDDFT) calculations using range-separated hybrid exchange–correlation functionals. Based on a non-self-consistent range-separated Hamiltonian, the method affords large-scale simulations at a fraction of the computational time of conventional hybrid TDDFT approaches. For typical benchmark molecules including N2, CO, C6H6, H2CO and the C2H4–C2F4 dimer, the method possesses the same level of accuracy as the conventional approaches for the valence, Rydberg, and charge-transfer excitation energies when compared to the experimental results. The method is used to determine π → π* excitations in both disordered and crystalline poly(3-hexylthiophene) (P3HT) conjugated polymers with more than six hundred atoms and it yields excitation energies and charge densities that are in excellent agreement with experiments. The simulation of the crystalline P3HT reveals that the phase of the wavefunctions could have an important effect on the excitation energy; a hypothesis based on π–π stacking is proposed to explain this novel effect in conjugated polymers.