DFT investigations of the vibrational spectra and translational modes of ice II

Abstract

The vibrational spectrum of ice II was investigated using the CASTEP code based on first-principles density functional theory (DFT). Based on good agreement with inelastic neutron scattering (INS), infrared (IR), and Raman experimental data, we discuss the translation, libration, bending, and stretching band using normal modes analysis method. In the translation band, we found that the four-bond and two-bond molecular vibration modes constitute three main peaks in accordance with INS ranging from 117 to 318 cm−1. We also discovered that the lower frequencies are cluster vibrations that may overlap with acoustic phonons. Whale et al. found in ice XV that some intramolecular vibrational modes include many isolated-molecule stretches of only one O–H bond, whereas the other O–H bond does not vibrate. This phenomenon is very common in ice II, and we attribute it to local tetrahedral deformation. The pathway of combining normal mode analysis with experimental spectra leads to scientific assignments.