Mixed Planewave and Localized Orbital Basis for Sparse-Stochastic Hybrid TDDFT
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arXiv
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| Autori principali: | , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| _version_ | 1866916892185198592 |
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| author | Chen, Kyle Li, Barry Y. Allen, Tucker Neuhauser, Daniel |
| author_facet | Chen, Kyle Li, Barry Y. Allen, Tucker Neuhauser, Daniel |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2506_17477 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Mixed Planewave and Localized Orbital Basis for Sparse-Stochastic Hybrid TDDFT Chen, Kyle Li, Barry Y. Allen, Tucker Neuhauser, Daniel Chemical Physics 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. |
| title | Mixed Planewave and Localized Orbital Basis for Sparse-Stochastic Hybrid TDDFT |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.17477 |