Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

Dar, Davood; Roy, Saswata; Maitra, Neepa T.

doi:10.1021/acs.jpclett.3c00122

Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

Journal Article · Mon Mar 27 00:00:00 EDT 2023 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.3c00122· OSTI ID:2530419

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Rutgers University, Newark, NJ (United States)

While time-dependent density functional theory has emerged as a method of choice for computing electronic spectra and response of molecules and materials, its reliability is hindered by the adiabatic approximation that is commonly made. In this work, we address one problematic aspect that arises from this approximation: an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. Here, we demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

View Accepted Manuscript (DOE)

Research Organization:: Rutgers University, Newark, NJ (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0020044

OSTI ID:: 2530419

Alternate ID(s):: OSTI ID: 2421405

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 13 Vol. 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Approximation
Excited states
Molecules
Resonance structures
Time dependant density functional theory

Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

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