Efficient evaluation of analytic vibrational frequencies in Hartree-Fock and density functional theory for periodic nonconducting systems

摘要

We report a method for the efficient evaluation of analytic energy second derivatives with respect to in-phase nuclear coordinate displacements within Hartree-Fock and Kohn-Sham density functional theories using Gaussian orbitals and periodic boundary conditions. The use of an atomic orbital formulation for all computationally challenging steps allows us to adapt the direct space fast multipole method for the Coulomb-type infinite summations. Our implementation also exploits the local character of the exact Hartree-Fock exchange in nonconducting systems. Exchange-correlation contributions are computed using extensive screening and fast numerical quadratures. We benchmark our scheme for in-phase vibrational frequencies of a trans-polyacetylene chain, a two-dimensional boron nitride sheet, and bulk diamond with the 6-31G~(**) basis set and various density functionals. A study of computational scaling with the size of the unit cell for trans-polyacetylene reveals subquadratic scaling for our scheme.