Parameterized Attenuated Exchange for Generalized TDHF@$v_W$ Applications
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arXiv
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| Autori principali: | , , , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| author | Li, Barry Y. Duong, Tim Allen, Tucker Bradbury, Nadine C. Caram, Justin R. Neuhauser, Daniel |
| author_facet | Li, Barry Y. Duong, Tim Allen, Tucker Bradbury, Nadine C. Caram, Justin R. Neuhauser, Daniel |
| contents | Building upon our previously developed time-dependent Hartree-Fock (TDHF)@$v_W$ method, based on many-body perturbation theory and specifically the Bethe-Salpeter Equation (BSE), we introduce a parameterization scheme for the attenuated exchange kernel, $v_W(|r - r'|)$. In the original method, $v_W$ was determined individually for each system via an efficient stochastic short-time TD Hartree propagation for the screened Coulomb interaction, $W(r,r')$. The new parameterization leverages photochemical similarities in exciton binding energies (or exchange interaction attenuation) among molecules with comparable static dielectric responses. We parameterize the inverse dielectric function using a low-order polynomial with error function apodization, calibrated on a few representative molecules, each with its own $v_W$. Using only 7 parameters, the parameterized $v_W$ is fully grid-independent and broadly applicable within a family of molecules. This enables TDHF@$v_W$ that retains BSE-level accuracy, achieving a mean absolute error of $\sim0.1$ eV compared to experimental optical gaps and representing a five- to ten-fold improvement over conventional TD density functional theory or TDHF while reducing the cost to that of standard TDHF. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2504_01285 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Parameterized Attenuated Exchange for Generalized TDHF@$v_W$ Applications Li, Barry Y. Duong, Tim Allen, Tucker Bradbury, Nadine C. Caram, Justin R. Neuhauser, Daniel Chemical Physics Building upon our previously developed time-dependent Hartree-Fock (TDHF)@$v_W$ method, based on many-body perturbation theory and specifically the Bethe-Salpeter Equation (BSE), we introduce a parameterization scheme for the attenuated exchange kernel, $v_W(|r - r'|)$. In the original method, $v_W$ was determined individually for each system via an efficient stochastic short-time TD Hartree propagation for the screened Coulomb interaction, $W(r,r')$. The new parameterization leverages photochemical similarities in exciton binding energies (or exchange interaction attenuation) among molecules with comparable static dielectric responses. We parameterize the inverse dielectric function using a low-order polynomial with error function apodization, calibrated on a few representative molecules, each with its own $v_W$. Using only 7 parameters, the parameterized $v_W$ is fully grid-independent and broadly applicable within a family of molecules. This enables TDHF@$v_W$ that retains BSE-level accuracy, achieving a mean absolute error of $\sim0.1$ eV compared to experimental optical gaps and representing a five- to ten-fold improvement over conventional TD density functional theory or TDHF while reducing the cost to that of standard TDHF. |
| title | Parameterized Attenuated Exchange for Generalized TDHF@$v_W$ Applications |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2504.01285 |