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 of 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 and indocyanine green dye families with a modifiable length of the polymethine bridge, leading to excitations ranging from visible to short-wave infrared. Our approach validates earlier observations on the importance of inclusion of medium range exchange for the exciton binding energy. Our resulting method, TDHF@vW, also achieves a mean absolute error on a par with MBPT at a computational cost on a par with local-functional TDDFT.
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14 October 2024
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October 08 2024
No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes
Nadine C. Bradbury
;
Nadine C. Bradbury
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Methodology, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095, USA
a)Author to whom correspondence should be addressed: [email protected]
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Barry Y. Li
;
Barry Y. Li
(Conceptualization, Data curation, Formal analysis, Investigation, Validation, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095, USA
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Tucker Allen
;
Tucker Allen
(Methodology, Software)
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095, USA
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Justin R. Caram
;
Justin R. Caram
b)
(Investigation, Supervision, Writing – review & editing)
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095, USA
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Daniel Neuhauser
Daniel Neuhauser
c)
(Methodology, Project administration, Software, Supervision, Writing – review & editing)
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095, USA
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a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 141101 (2024)
Article history
Received:
June 17 2024
Accepted:
August 15 2024
Citation
Nadine C. Bradbury, Barry Y. Li, Tucker Allen, Justin R. Caram, Daniel Neuhauser; No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes. J. Chem. Phys. 14 October 2024; 161 (14): 141101. https://doi.org/10.1063/5.0223783
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