First-principles evaluation of the second harmonic generation response of reference organic and inorganic crystals

Using the CRYSTAL17 package at the coupled-perturbed Kohn-Sham (CPKS) level, periodic boundary conditions first-principles calculations are enacted to predict the second harmonic generation second-order nonlinear optical (NLO) susceptibility, χ⁽²⁾, values of six historical NLO crystals. This selection allowed the comparison between state-of-the-art calculations and experiment. Several computational aspects are tackled to define conditions where the results are converged with respect to the range of lattice summations, to the number of k-points in the first Brillouin zone, to the order of the multipole expansions for evaluating the long-range part of the electrostatic interactions, as well as to the atomic basis set size. A valence triple zeta basis set supplemented with polarization functions has been selected. Then, χ⁽²⁾ calculations have been performed using a range of exchange-correlation functionals (XCFs). Results show the large impact of the amount of Hartree-Fock (HF) exchange on the amplitude but also on the sign on the χ⁽²⁾ tensor components. To a given extent, these amplitude effects are consistent with results on molecules, but the sign reversal effects and the non-monotonic behavior of the χ⁽²⁾ tensor components as a function of the amount of HF exchange are scarcely found for molecules. Then, using the recommended range-separated hybrid XCFs, the CPKS scheme leads to good agreement with experimental data for potassium dihydrogenophosphate, urea, and χ_ZXX ⁽²⁾ of LiNbO₃. The agreement is more questionable for χ_ZZZ ⁽²⁾ of LiNbO₃ whereas it remains poor for ammonium dihydrogenophosphate and 2-methyl-4-nitroaniline, with large underestimations by about a factor of 3, opening a path to further fine-tuning of the ranges of inclusion of HF exchange.