Analytical infrared intensities for periodic systems with local basis sets

We report a method for the efficient evaluation of analytic infrared intensities within a 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($p$-phenylene vinylene).

Figure 1

Schematic structure of the one-dimensional water chain. Optimized parameter values are listed in Table .

Figure 2

Poly($p$-phenylene vinylene) (PPV).

Figure 3

IR spectra of PPV. The experimental spectrum (bottom graph) is based on data given in Ref. 34. The calculated spectra were obtained by using a Lorentzian broadening with a $10{\text{cm}}^{-1}$ width.