Infrared and Raman line shapes for ice Ih. II. H2O and D2O

Abstract

We present a theoretical study of infrared and Raman line shapes of polycrystalline and single crystal ice Ih, for both water and heavy water, at 1, 125, and 245 K. Our calculations involve a mixed quantum/classical approach, a new water simulation model with explicit three-body interactions, transition frequency and dipole maps, and intramolecular and intermolecular vibrational coupling maps. Our theoretical spectra are in reasonable agreement with experimental spectra (available only near the two higher temperatures). We trace the origins of the different spectral peaks to weak and strong intermolecular couplings. We also discuss the delocalization of the vibrational eigenstates in terms of the competing effects of disorder and coupling.