Infrared Spectra of Ices Ih and Ic in the Range 4000 to 350 cm—1

Abstract

The infrared spectra of Ice Ih made from H2O, D2O, a mixture of 95% H2O and 5% D2O, and a mixture of 5% H2O and 95% D2O, and of Ice Ic made from H2O, D2O, and a mixture of 95% H2O and 5% D2O, have been recorded in the region 4000 to 350 cm—1 using low-temperature mulling techniques developed in these laboratories. The Ice Ic was made by transformation of Ices II and III, and was authenticated by its x-ray diffraction powder pattern. The spectra of Ices Ih and Ic are identical within experimental error. The spectra of Ice Ih, while similar in their main features to those reported by earlier workers, differ significantly in detail, probably largely because much of the previous work, particularly on D2O ice, has been done with partly vitreous ice. The usual interpretation of the bands in terms of the v1, v2, v3, and vR vibrations of isolated molecules is greatly oversimplified because intermolecular coupling is important. There are at least six (five infrared and one Raman) bands due to O—D stretching vibrations in the spectrum of D2O Ice I, but the detailed origin is unknown. The breadth of the O–H and O—D stretching bands of HDO in dilute solution in D2O and H2O is interpreted as indicating a disarrangement of the oxygen positions due to the disorder of the hydrogen atoms.

Dispersion Interactions and Vibrational Effects in Ice as a Function of Pressure: A First Principles Study

“…PBE and vdW-DF2 results exhibit several differences in the low P phase. The stretching mode frequencies are higher in ice XI and I c when using vdW-DF2, consistent with results obtained for liquid water [26] and in better agreement with the peaks observed in the measured IR spectra [27], at 3150, 3220, and 3380 cm À1 . Differences between the phonon density of states of ice VIII obtained at the PBE and vdW-DF2 level of theory are instead minor.…”

Film Growth of Ice by Vapor Deposition at 128−185 K Studied by Fourier Transform Infrared Reflection−Absorption Spectroscopy: Evolution of the OH Stretch and the Dangling Bond with Film Thickness

“…Figure 11 shows the experimental spectra for relatively thick films obtained by water vapor deposition at 1 × 10 -6 Torr for 3.5, 20.5, and 33.5 min and at 5 × 10 -6 Torr for 11 min with the substrate held at 131 K, which correspond to nc-ice film thicknesses of 110, 450, 750, and 1250 nm, respectively, as estimated by the optical interference method. As before, the features near 1655 and 2230 cm -1 (Figure 11a) can be assigned, respectively, as the OH bending band and the combination band of the OH bending and hindered rotation modes; 48 and these features remain essentially "stationary" in peak positions with increasing film thickness. The spectral evolution of the OH stretch (near 3430 cm -1 for the 110-nm-thick film shown in Figure 11a) with growth of the nc-ice film is also similar to that observed for the pc-ice film growth ( Figure 5).…”

“…In addition to the OH stretch features at 3410, 3325, and 3180 cm -1 shown in Figure 5a, the features near 1630 and 2240 cm -1 have been attributed to the OH bending band (ν 2 ) possibly coupled with the first overtone (2ν R ) of the hindered rotational lattice mode (ν R ≈ 850 cm -1 37 ) and to the combination band of the OH bending and hindered rotational mode and/or the second overtone (3ν R ) of the hindered rotational mode, respectively. 37,48 With the exception of the feature at 2255 cm -1 for the 1200-nm-thick film, these two vibrational bands are found to be essentially stationary with a general increase in the spectral intensity with increasing film thickness ( Figure 5). Furthermore, there is excellent agreement in the OH stretch region between the experimental spectrum and the corresponding Fresnel spectrum of a pc-ice film with a thickness of 100 nm ( Figure 5a).…”

Two-dimensional infrared spectroscopy of isotope-diluted ice Ih

“…There has been a long standing debate concerning the lineshape of neat (H 2 O and D 2 O) ice Ih, 23,28,68 which exhibits much more complex structure than that of isotope diluted ice Ih. One explanation of the complex linear spectra is based on the strong excitonic coupling between individual water molecules.…”

“…[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.…”