Mixed Planewave and Localized Orbital Basis for Sparse-Stochastic Hybrid TDDFT

2025/06/20 by Chen, Kyle, Li, Barry Y., Allen, Tucker +1 · 1 citation
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences

paper · doi:10.48550/arxiv.2506.17477

Abstract

We present a mixed basis-set approach to obtain optical absorption spectra within a generalized Kohn-Sham time-dependent density functional theory framework. All occupied valence molecular orbitals (MOs) are expanded in a plane-wave (PW) basis, while unoccupied MOs are derived primarily from localized atomic basis functions. The method accelerates spectral convergence when compared to fully PW-based simulations, with a 2-3 fold reduction in the number of unoccupied MOs entering the Casida equation. The mixed-basis is placed on a common real-space grid, enabling our previously developed deterministic/sparse-stochastic evaluation of the exact exchange operator (J. Chem. Theory Comput. 2023, 19, 9239-9247). This chemically intuitive and computationally efficient approach is validated across various molecular systems, including π-conjugated polymethine dyes, aromatic hydrocarbons, and a chlorophyll monomer.

Citations

• Deterministic/Fragmented-Stochastic Exchange for Large Scale Hybrid DFT Calculations
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Cited by

• A Snapshot of Time-Dependent Density-Functional Theory

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