Benchmarking DFT-based excited-state methods for intermolecular charge-transfer excitations.

Abstract

Intermolecular charge-transfer is a highly important process in biology and energy-conversion applications where generated charges need to be transported over several moieties. However, its theoretical description is challenging since the high accuracy required to describe these excited states must be accessible for calculations on large molecular systems. In this benchmark study, we identify reliable low-scaling computational methods for this task. Our reference results were obtained from highly accurate wavefunction calculations that restrict the size of the benchmark systems. However, the density-functional theory based methods that we identify as accurate can be applied to much larger systems. Since targeting charge-transfer states requires the unambiguous classification of an excited state, we first analyze several charge-transfer descriptors for their reliability concerning intermolecular charge-transfer and single out the charge-transfer distance calculated based on the variation of electron density upon excitation (DCT) as an optimal choice for our purposes. In general, best results are obtained for orbital-optimized methods and among those, the maximum overlap method proved to be the most numerically stable variant when using the initial MOs as reference orbitals. Favorable error cancellation with optimally-tuned range-separated hybrid functionals and a rather small basis set can provide an economical yet reasonable wavefunction when using time-dependent density functional theory, which provides relevant information about the excited-state character to be used in the orbital-optimized methods. The qualitative agreement makes these fast calculations attractive for high-throughput screening applications.