Theoretical study of the OH/OD stretching regions of the vibrational spectra of ice Ih

Abstract

In this paper we present results of our theoretical studies of the vibrational spectra of ice Ih in the stretching mode frequency range. They include simulation of the infrared and Raman spectra for the OH and OD stretching regions, the effects of a full range of isotopic dilution on the spectra (including polarized Raman spectra) and computational modeling of the observed influence of each dilution step on the properties of vibrationally excited states and on the infrared and Raman spectra. In our calculations we included effects of frequency lowering due to hydrogen bonding, and of intramolecular and intermolecular coupling between bonds. In the crystalline isotopomers the properties of the vibrationally excited states and of the spectra are determined by a complex interplay between the size distributions of the embedded clusters and the intermolecular and intramolecular couplings.

Vibrational Line Shapes, Spectral Diffusion, and Hydrogen Bonding in Liquid Water

“…We have already seen that using these models at higher or lower temperatures even for liquid water leads to discrepancies. We note that a significant amount of important theoretical work on ice has already been published by Buch and others [71,72,111,175,176].…”

Raman and IR Spectra of Ice Ih and Ice XI with an Assessment of DFT Methods

“…[24][25][26][27][28][29] Only a few works on ice XI have been carried out until now. [30][31][32][33][34][35] The polarized Raman spectra of ice XI have been measured based on samples obtained from KOH-doped ice and the vibrational modes in the translational, librational, bending, and stretching region have been assigned by Abe and Shigenari.…”

The microscopic origin of the anomalous isotopic properties of ice relies on the strong quantum anharmonic regime of atomic vibration

“…[27][28][29][30] The vibrational properties of ice have been widely investigated by using mainly Raman, Infrared, and neutron spectroscopy. [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] Alongside experimental works, several theoretical studies focused on the librational modes [46][47][48][49] and on the OH stretching bands, 50,51 where the authors were able to calculate linewidths in good agreement with experimental data but shifted peak positions. The low-energy modes computed using standard ab initio techniques display a severe disagreement with experiments.…”