A detailed assignment of the O–H stretching bands of ice I

Abstract

E. WHALLEY. Can. J. Chem. 55,3429 (1977). A detailed assignment of the infrared and Raman 0-H stretching bands of disordered ice Ih and Ic is proposed. It is based on the assumptions that the spectra of disordered ice Ic are closely related to those of ordered ice Ic, and that the spectra of the as yet unrealized ordered ice Ic can be predicted from the spectra of ice VIII. The supposed similarity between the spectra of ordered and disordered ice Ic is justified by the observed similarity of the spectra of ice VIII and VII, which are respectively ordered and disordered forms of the same structure and are closely related to ordered and disordered ice Ic. The assignment takes into account the intermolecular coupling, which is particularly strong for the v, vibrations but weak for the v,, and the TO-LO splitting, particularly of the v, vibrations, which is shown to be required by the high infrared intensity. The infrared and Raman bands of amorphous ice have been assigned by analogy with the assignments ofice I. E. WHALLEY. Can. J. Chem. 55, 3429 (1977). On propose une attribution detaillee des bandes d'elongation 0 -H en ir et en Raman des glaces desordonnees Ih et Ic. Cette attribution est basee sur l'hypothese que le spectre de la glace desordonnee Ic resemble beaucoup A celle de la glace ordonnee Ic et que le spectre qui n'a pas encore kt6 obtenu pour la glace ordonnee Ic peut 2tre predit A partir du spectre de la glace VIII.Les similarites supposees entre les spectres des glaces Ic ordonnee et dtsordonnee sont justifiees par la similarite observee dans les spectres des glaces VIII et VII qui sont respectivement les formes ordonnees et desordonnees de la mCme structure et sont tres reliees aux glaces Ic ordonnee et desordonnee. L'attribution rend compte du couplage intermoleculaire, qui est particulierement fort pour les vibrations v, mais faible pour v,, et le dedoublement TO-LO, en particulier des vibrations v,, qu'on demontre Ctre necessaire par consequence de la grande intensite du spectre infrarouge. On a attribue les bandes infrarouges et Raman de la glace amorphe par analogie avec les attributions de la glace I.[Traduit par le journal]

FTIR Studies of Annealing Processes in Low Temperature Pure and Mixed Amorphous Ice Samples

“…Even though LO-TO splittings in disordered materials as vitreous silica and germania are known to have been observed, 40 the high concentration found here of Ar/Ne guest molecules is expected to strongly minimize this mode coupling. Thus, the increase of the 3300 and 3450 cm -1 bands speaks against their assignments to ν 1 + ν t 30 or to ν 3 + LO 35 and supports the more general one by Rice et al 36,37 Similar results are obtained by curve-fitting calculations. In addition, these procedures emphasize the existence of a low-frequency component around 3150 cm -1 also in the mixed ice samples.…”

“…Also its band peak is the closest in position to those of Ic ice infrared wavenumber of 3206 cm -1 7 or the 3220 cm -1 Raman band. 35 Of the three ices from premixed samples, the Ne/H 2 O ( Figure 1D) and Ar/H 2 O ( Figure 1E) bands show four partly resolved components, while the 1:10 CO/H 2 O ( Figure 1F) ice demonstrates an unresolved "amorphous" band shape. It is quite certain that a considerable amount of the added gases is deposited as an external layer.…”

Depositional ice nucleation on solid ammonium sulfate and glutaric acid particles

“…These results indicate that depositional ice nucleation on solid ammonium sulfate does not have a significant temperature dependence over this temper- Panel (A) shows Raman spectra taken during a depositional nucleation experiment on ammonium sulfate. Humidified air was slowly introduced into the sample cell and ice formation was observed (panel A, top spectrum) at 218.1 K. Peak a corresponds to the ν(OH) band of water ice at 3132 cm −1 (Whalley, 1977) . Although the water ice signal is strong, the sulfate vibrational signature from the ammonium sulfate ice nucleus is clearly visible at 972 cm −1 (marked as c).…”

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

“…[24][25][26][27] Furthermore, the linear IR and Raman spectra of ice Ih have been investigated throughout the whole frequency range. [28][29][30][31][32][33][34] Nonlinear spectroscopic studies such as pump-probe, hole-burning, photon-echo or 2D IR spectroscopy, on the other hand, remained much more scarce. In particular, the nonlinear infrared spectroscopy of the OH stretch vibration (or correspondingly the OD stretch vibration) is of interest, since the local molecular environment directly affects its frequency, line shape and dynamics.…”