We describe our implementation of a fully analytical scheme, based on the 2n + 1 rule, for computing the coupled perturbed Hartree Fock and Kohn-Sham dynamic first hyperpolarizability tensor β(−ωσ;ω1,ω2) of periodic 1D (polymer), 2D (slab), and 3D (crystal) systems in the CRYSTAL code [R. Dovesi et al., Int. J. Quantum Chem. 114, 1287 (2014)], which utilizes local Gaussian type basis sets. The dc-Pockels (dc-P) and second harmonic generation (SHG) tensors are included as special cases. It is verified that (i) symmetry requirements are satisfied; (ii) using LiF as an example, the infinite periodic polymer result agrees with extrapolated finite oligomer calculations and, likewise, for the build-up to a 2D slab and a 3D crystal; (iii) the values converge to the static case for low frequencies; and (iv) the Bishop-deKee dispersion formulas relating dc-P, SHG, and general processes are reproduced through quartic terms. Preliminary SHG calculations on multi-layer MoS2 satisfactorily reproduce experimental data.

Calculation of the dynamic first electronic hyperpolarizability β (- ω σ; ω 1, ω 2) of periodic systems. Theory, validation, and application to multi-layer MoS2

MASCHIO, LORENZO;DOVESI, Roberto
2015

Abstract

We describe our implementation of a fully analytical scheme, based on the 2n + 1 rule, for computing the coupled perturbed Hartree Fock and Kohn-Sham dynamic first hyperpolarizability tensor β(−ωσ;ω1,ω2) of periodic 1D (polymer), 2D (slab), and 3D (crystal) systems in the CRYSTAL code [R. Dovesi et al., Int. J. Quantum Chem. 114, 1287 (2014)], which utilizes local Gaussian type basis sets. The dc-Pockels (dc-P) and second harmonic generation (SHG) tensors are included as special cases. It is verified that (i) symmetry requirements are satisfied; (ii) using LiF as an example, the infinite periodic polymer result agrees with extrapolated finite oligomer calculations and, likewise, for the build-up to a 2D slab and a 3D crystal; (iii) the values converge to the static case for low frequencies; and (iv) the Bishop-deKee dispersion formulas relating dc-P, SHG, and general processes are reproduced through quartic terms. Preliminary SHG calculations on multi-layer MoS2 satisfactorily reproduce experimental data.
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http://scitation.aip.org/content/aip/journal/jcp
Physics and Astronomy (all); Physical and Theoretical Chemistry
Maschio, Lorenzo; Rérat, Michel; Kirtman, Bernard; Dovesi, Roberto
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/1558371
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