Sparse-Stochastic Fragmented Exchange for Large-Scale Hybrid Time-Dependent Density Functional Theory Calculations

Abstract

We extend our recently developed sparse-stochastic fragmented exchange formalism for ground-state near-gap hybrid DFT to calculate absorption spectra within linear-response time-dependent generalized Kohn−Sham DFT (LR-GKS-TDDFT) for systems consisting of thousands of valence electrons within a grid-based/plane-wave representation. A mixed deterministic/fragmented-stochastic compression of the exchange kernel, here using long-range explicit exchange functionals, provides an efficient method for accurate optical spectra. Both real-time propagation as well as frequency-resolved Casida-equation-type approaches for spectra are presented, and the method is applied to large molecular dyes.