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Title: Calculation of the dynamic first electronic hyperpolarizability β(−ω{sub σ}; ω{sub 1}, ω{sub 2}) of periodic systems. Theory, validation, and application to multi-layer MoS{sub 2}

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(−ω{sub σ}; ω{sub 1}, ω{sub 2}) 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 MoS{sub 2} satisfactorily reproduce experimental data.
Authors:
;  [1] ;  [2] ;  [3]
  1. Dipartimento di Chimica and NIS (Nanostructured Interfaces and Surfaces) Centre, Università di Torino, via Giuria 5, I-10125 Torino (Italy)
  2. Equipe de Chimie Physique, IPREM UMR5254, Université de Pau et des Pays de l’Adour, 64000 Pau (France)
  3. Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States)
Publication Date:
OSTI Identifier:
22493390
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; C CODES; COMPUTER CALCULATIONS; CRYSTALS; HARMONIC GENERATION; HARTREE-FOCK METHOD; LAYERS; LITHIUM FLUORIDES; MOLYBDENUM SULFIDES; PERIODICITY; POLARIZABILITY; POLYMERS; TENSORS; VALIDATION