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IOP Publishing, Electronic Structure, 4(4), p. 044004, 2022

DOI: 10.1088/2516-1075/aca859

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Efficient Kohn–Sham density-functional theory implementation of isotropic spectroscopic observables associated with quadratic response functions

Journal article published in 2022 by Karan Ahmadzadeh ORCID, Xin Li ORCID, Zilvinas Rinkevicius ORCID, Patrick Norman ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

Abstract For general exchange–correlation functionals with a dependence on the local spin densities and spin-density gradients, we provide computationally tractable expressions for the tensor-averaged quadratic response functions pertinent to the experimental observables in second-harmonic generation (SHG). We demonstrate how the tensor-averaged quantities can be implemented with reference to a derived minimal number of first- and second-order perturbed Fock matrices. Our consideration has the capability of treating a situation of resonance enhancement as it is based on damped response theory and allows for the evaluation of tensor-averaged resonant-convergent quadratic response functions using only ∼25% (one-photon off-resonance regions) and ∼50% (one-photon resonance regions) of the number of auxiliary Fock matrices required when explicitly calculating all the needed individual tensor components. Numerical examples of SHG intensities in the one-photon off-resonance region are provided for a sample of makaluvamine derivatives recognized for their large nonlinear optical responses as well as a benchmark set of small- and medium-sized organic molecules.