Calculation of the first static hyperpolarizability tensor of three-dimensional periodic compounds with a local basis set: A comparison of LDA, PBE, PBE0, B3LYP, and HF results

Roberto Orlando; Valentina Lacivita; Radovan Bast; Kenneth Ruud

doi:10.1063/1.3447387

Calculation of the first static hyperpolarizability tensor of three-dimensional periodic compounds with a local basis set: A comparison of LDA, PBE, PBE0, B3LYP, and HF results

J Chem Phys. 2010 Jun 28;132(24):244106. doi: 10.1063/1.3447387.

Authors

Roberto Orlando¹, Valentina Lacivita, Radovan Bast, Kenneth Ruud

Affiliation

¹ Dipartimento di Scienze e Tecnologie Avanzate, Università del Piemonte Orientale, Viale T. Michel 11, Alessandria 15121, Italy.

PMID: 20590180
DOI: 10.1063/1.3447387

Abstract

The computational scheme for the evaluation of the second-order electric susceptibility tensor in periodic systems, recently implemented in the CRYSTAL code within the coupled perturbed Hartree-Fock (HF) scheme, has been extended to local-density, gradient-corrected, and hybrid density functionals (coupled-perturbed Kohn-Sham) and applied to a set of cubic and hexagonal semiconductors. The method is based on the use of local basis sets and analytical calculation of derivatives. The high-frequency dielectric tensor (epsilon(infinity)) and second-harmonic generation susceptibility (d) have been calculated with hybrid functionals (PBE0 and B3LYP) and the HF approximation. Results are compared with the values of epsilon(infinity) and d obtained from previous plane-wave local density approximation or generalized gradient approximation calculations and from experiment. The agreement is in general good, although comparison with experiment is affected by a certain degree of uncertainty implicit in the experimental techniques.