Mid-infrared spectra of deuterated ices at 10°K and interpretation of the OD stretching bands of ices II and IX

Abstract

The infrared absorption bands due to the OD stretching vibrations of DP and HDO, and to the DP rotational vibrations, in the ordered forms of ice, ice II and ice IX, change little between 100 and lOoK. The frequencies and relative intensities of the zero-wave-vector OD stretching vibrations of these phases have been calculated in the harmonic and bond-moment approximations, and explain the main features of these bands. The features are less well resolved than is expected for an ordered molecular crystal, and this "hydrogen bonding effect" is attributed primarily to Fermi resonance between the fundamental states of the OD stretching vibrations and the isoenergetic continuum of high-order, overtone, and combination states of lower-frequency vibrations. The frequency of the OD stretching vibrations of HDO molecules isolated in H 2 0 ice Ih at lOOK is 2413.5 ± I em-I.

Effect of dispersion correction on the Au(1 1 1)-H2O interface: A first-principles study

“…65 Yet, it has been reported that the hydrogen bond strength also decreases when the pressure increases. [66][67][68] In the present setup one might think that the observed shifts could be induced by an expansion of the slab in the direction of the surface normal. Over the course of the simulation the surface atoms most certainly do expand and contract.…”

Effects of salts of the Hofmeister series on the hydrogen bond network of water

“…A great deal is known about the relationship between hydrogen bond geometry and O-H stretching frequencies from the various forms of ice, thus the relationship between O-H stretch frequency and hydrogen bond geometry is well characterized for crystalline forms of water [52–64]. Based on such data and on additional spectral analysis and ab initio calculations, Walrafen assigned specific frequencies for the two structural components of the water O-H stretch: 3350 cm −1 and 3440 cm −1 for linear and bent hydrogen bonds, respectively [65].…”

Two-dimensional infrared spectroscopy of neat ice Ih

“…[3][4][5][6][7][8][9][10][11] Still the interpretation of the vibrational spectra of ice I h has been subject to a long standing debate. 9,[12][13][14][15][16][17][18][19][20][21][22][23] It has, for example, been suggested that the lowest frequency peak in the Raman spectrum should be assigned to globally in-phase symmetric stretch, while the rest should be interpreted in terms of out-of-phase symmetric and antisymmetric stretches with longitudinal and transverse optical (LO-TO) phonon splitting. 15 Others have concluded that the spectral features arise from an interplay between intra-and intermolecular coupling, that an interpretation in terms of the molecular symmetric and asymmetric stretch modes is meaningless, and that the LO-TO splitting had negligible effect on the spectral line shape.…”