Analytical infrared intensities for periodic systems with local basis sets

TL;DR

This paper introduces an efficient method for calculating analytic infrared intensities in periodic systems using Gaussian orbitals and Berry phase, demonstrated on molecular chains.

Contribution

It presents a novel approach combining Berry phase discretization with density functional theory for periodic IR intensity calculations.

Findings

Accurate IR intensities for 1D water chains

Effective evaluation of dipole moments in periodic systems

Benchmark results for polymer-like chains

Abstract

We report a method for the efficient evaluation of analytic infrared (IR) intensities within generalized Kohn-Sham density functional theory using Gaussian orbitals and periodic boundary conditions. A discretized form of the Berry phase is used to evaluate a periodic dipole moment and its derivatives with respect to in-phase nuclear coordinate displacements. Benchmark calculations are presented for one-dimensional chains of water molecules and poly(paraphenylenevinylene).