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DOE OSTI · 2530419

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

Dar, Davood·Roy, Saswata·Maitra, Neepa T.
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Abstract

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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYApproximationExcited statesMoleculesResonance structuresTime dependant density functional theory

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Dar, Davood, Roy, Saswata, Maitra, Neepa T.. 2023-03-27. Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory. https://doi.org/10.1021/acs.jpclett.3c00122

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