Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. II. Validation and comparison with experiments

L. Maschio , B. Kirtman , Michel Rérat (1) , R. Orlando , Roberto Dovesi

1 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

In this work, we validate a new, fully analytical method for calculating Raman intensities of periodic systems, developed and presented in Paper I [L. Maschio, B. Kirtman, M. Rérat, R. Orlando, and R. Dovesi, J. Chem. Phys. 139, 164101 (2013)]. Our validation of this method and its implementation in the CRYSTAL code is done through several internal checks as well as comparison with experiment. The internal checks include consistency of results when increasing the number of periodic directions (from 0D to 1D, 2D, 3D), comparison with numerical differentiation, and a test of the sum rule for derivatives of the polarizability tensor. The choice of basis set as well as the Hamiltonian is also studied. Simulated Raman spectra of α-quartz and of the UiO-66 Metal-Organic Framework are compared with the experimental data. © 2013 AIP Publishing LLC.

Domaines: Chimie théorique et/ou physique

L. Maschio, B. Kirtman, Michel Rérat, R. Orlando, Roberto Dovesi. Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. II. Validation and comparison with experiments. Journal of Chemical Physics, 2013, 139 (16), ⟨10.1063/1.4824443⟩. ⟨hal-01610567⟩