The calculation of the vibrational frequencies of crystalline compounds and its implementation in the CRYSTAL code

Abstract

The problem of numerical accuracy in the calculation of vibrational frequencies of crystalline compounds from the hessian matrix is discussed with reference to alpha-quartz (SiO(2)) as a case study and to the specific implementation in the CRYSTAL code. The Hessian matrix is obtained by numerical differentiation of the analytical gradient of the energy with respect to the atomic positions. The process of calculating vibrational frequencies involves two steps: the determination of the equilibrium geometry, and the calculation of the frequencies themselves. The parameters controlling the truncation of the Coulomb and exchange series in Hartree-Fock, the quality of the grid used for the numerical integration of the Exchange-correlation potential in Density Functional Theory, the SCF convergence criteria, the parameters controlling the convergence of the optimization process as well as those controlling the accuracy of the numerical calculation of the Hessian matrix can influence the obtained vibrational frequencies to some extent. The effect of all these parameters is discussed and documented. It is concluded that with relatively economical computational conditions the uncertainty related to these parameters is smaller than 2-4 cm(-1). In the case of the Local Density Approximation scheme, comparison is possible with recent calculations performed with a Density Functional Perturbation Theory method and a plane-wave basis set.

Low-frequency Raman study of the ferroelectric phase transition in a layeredCuCl4-based organic-inorganic hybrid

“…64 with the Perdew-BurkeErnzerhof (PBE) functional] using the CRYSTAL (Refs. [65][66][67][68] package with the Doll basis set for Cu, 69 the Aprà basis set for Cl, 70 and the 6-21G* basis set for C/N/H (Refs. 71-73) (CRYSTAL basis set web page 74 ).…”

Ab initio LCAO study of the atomic, electronic and magnetic structures and the lattice dynamics of triclinic CuWO4

“…The phonon frequencies at the centre of the Brillouin zone (the Γ-point) in the AFM phase were calculated using the direct (frozen-phonon) method [24,37]. Their values for the three hybrid DFT-HF functionals (PBE0-13%, WCGGA-PBE-16% and PBE0-25%) are reported in Tables 3 and 4 for the Raman-active modes and the infrared (IR)-active modes, respectively.…”

High resolution electron energy loss spectroscopy of clean and hydrogen covered Si(001) surfaces: First principles calculations

“…The Crystal code used in this work employs a finite displacement phonon method 36,37 to calculate the dynamical matrix for point phonons. Born effective charge tensors in Crystal are obtained using a Berry phase method.…”