Vibrational spectra and nonlinear optical coefficients of rhombohedralCsGeX3halide compounds withX=I, Br, Cl

Abstract

The zone-center phonons are calculated for rhombohedral $\mathrm{CsGe}{X}_{3}$ compounds with $X=\mathrm{I}$, Br, Cl using density functional perturbation theory in a plane-wave pseudopotential method. The infrared absorption and reflection spectra are simulated and show that the absorption has a strong contribution from the LO as well as TO modes. Both the lowest and highest IR active modes have strong oscillator strengths for each symmetry (${A}_{1}$ and $E$) and correspond to motions of either the Cs or Ge ions relative to the halogen ions. respectively. The intermediate modes have low oscillator strength because their mode pattern shows less clearly a dipole pattern. The polarization dependent Raman spectra for various backscattering configurations are simulated. Only the highest modes of each symmetry have a strong Raman intensity. The results for the Raman spectra are found to be in good agreement with the available experimental data for polycrystalline films when averaging over directions. The Born effective charges and high and low frequency dielectric tensors as well as the second-order nonlinear optical coefficients are calculated. The ratio of the static to the high-frequency dielectric constants are extremely high and analyzed in terms of the contribution of each mode to the Lyddane-Sachs-Teller relation. The nonlinear optical coefficients decrease strongly from I to Br to Cl in reverse order of the band gaps and are found to be consistent with available experimental results.