No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes
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| Main Authors: | , , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866914841030033408 |
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| author | Bradbury, Nadine C. Li, Barry Y. Allen, Tucker Caram, Justin R. Neuhauser, Daniel |
| author_facet | Bradbury, Nadine C. Li, Barry Y. Allen, Tucker Caram, Justin R. Neuhauser, Daniel |
| contents | We introduce an individually fitted screened-exchange interaction for the time-dependent Hartree-Fock (TDHF) method and show that it resolves the missing binding energies in polymethine organic dye molecules compared to time-dependent density functional theory (TDDFT). The interaction kernel, which can be thought as a dielectric function, is generated by stochastic fitting to the screened-Coulomb interaction of many-body perturbation theory (MBPT), specific to each system. We test our method on the flavylium (Flav) and indocyanine green (ICG) dye families with a modifiable length of the polymethine bridge, leading to excitations ranging from the visible to short-wave infrared (SWIR). Our approach validates earlier observations on the importance of inclusion of medium range exchange for the exciton binding energy. Our resulting method, TDHF@$v_W$, also achieves a mean absolute error on par with MBPT at a computational cost on par with local-functional TDDFT. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2406_09544 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes Bradbury, Nadine C. Li, Barry Y. Allen, Tucker Caram, Justin R. Neuhauser, Daniel Chemical Physics We introduce an individually fitted screened-exchange interaction for the time-dependent Hartree-Fock (TDHF) method and show that it resolves the missing binding energies in polymethine organic dye molecules compared to time-dependent density functional theory (TDDFT). The interaction kernel, which can be thought as a dielectric function, is generated by stochastic fitting to the screened-Coulomb interaction of many-body perturbation theory (MBPT), specific to each system. We test our method on the flavylium (Flav) and indocyanine green (ICG) dye families with a modifiable length of the polymethine bridge, leading to excitations ranging from the visible to short-wave infrared (SWIR). Our approach validates earlier observations on the importance of inclusion of medium range exchange for the exciton binding energy. Our resulting method, TDHF@$v_W$, also achieves a mean absolute error on par with MBPT at a computational cost on par with local-functional TDDFT. |
| title | No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2406.09544 |