Phonon coupling of water monomers in a solid nitrogen matrix

Abstract

The infrared absorption spectra of the H2O, HDO, and D2O monomers isolated in solid N2 have been recorded at various temperatures between 4 and 30 K. A study of the absorption features of the ν1, ν2, and ν3 vibrational modes for each monomer shows their optical line shapes to be strongly temperature dependent. For all three modes, a decrease in the absorption amplitude and a proportional broadening of the linewidth was observed with increasing temperature, while the integrated absorbance remained constant. These observations were explained in terms of phonon coupling, by which high frequency intramolecular modes decay by exciting matrix phonons. Fits of the linewidth for the lowest frequency ν2 vibrational mode to the predicted vibrational relaxation rate in a solid medium gave average phonon mode frequencies consistent with the Debye frequency for solid N2.