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arxiv 2211.09885 v3 pith:HOM47RZG submitted 2022-11-17 physics.chem-ph

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

classification physics.chem-ph
keywords quadraticresponseapproximationdensitydivergenceexcitedfunctionalprobabilities
verification ladder T0 review T1 audit T2 compute T3 formal T4 reserved
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The adiabatic approximation in time-dependent density functional theory (TDDFT) is known to give 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. We demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

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