Infrared and Raman line shapes for ice Ih. I. Dilute HOD in H(2)O and D(2)O.

Vibrational spectroscopy of ice Ih provides information about structure, dynamics, and vibrational coupling in this important substance. Vibrational spectra are simplified for HOD in either H(2)O or D(2)O, as in these instances the OD or OH stretch, respectively, functions as a local chromophore. As a first step in providing a theoretical treatment of the vibrational spectroscopy for the fully coupled system (H(2)O or D(2)O), herein we calculate the infrared and Raman spectra for the isotopically substituted systems. The calculation involves a classical molecular dynamics simulation using a new water model, an initial proton-disordered ice configuration, and ab initio based transition frequency, dipole, and polarizability maps. Our theoretical results are in reasonable agreement with experiment, and from our results we provide molecular and physical interpretations for the spectral features.