Polarized Raman spectra for the full range of isotopic dilution for ice I/sub c/ and amorphous ice: Mixtures of intact H/sub 2/O and D/sub 2/O

Journal Article · Wed Feb 01 04:00:00 EST 1989 · J. Chem. Phys.; (United States)

OSTI ID:6565568

Devlin, J P

The 90 K polarized Raman scattering of thin films of ice I/sub c/ and ice I/sub a/ containing mixtures of intact H/sub 2/O and D/sub 2/O have been measured using the interference-enhanced internal-reflection technique. The effects of isotopic dilution reported for samples with a D/sub 2/O content ranging from 0% to 100% are consistent with the commonly held view that intermolecular coupling produces collective vibrational modes that determine the appearance of the Raman spectra in the stretching mode region of crystalline and amorphous ice. The convergence of bands produced by the collective modes on the isotopically decoupled mode frequencies of both ..nu../sub 1/ and ..nu../sub 3/ is displayed in this study. Bands at 3323 and 3209 cm/sup -1/ in the anisotropic scattering of protiated ice I/sub c/ are shown to converge on the decoupled antisymmetric stretch frequency of 3370 cm/sup -1/. The gradual shift of the dominant isotropic scattering at 3085 cm/sup -1/ towards the frequency of the decoupled ..nu../sub 1/ mode is also revealed, with bands for the first stage in the evolution of the in-phase ..nu../sub 1/ collective mode, i.e., the neighbor coupled mode, observed at 3180 (H/sub 2/O) and 2340 cm/sup -1/ (D/sub 2/O). The data also suggest that the shift of the in-phase coupled ..nu../sub 1/ band begins with the first traces of added diluent, a behavior that indicates a macroscopic extension of the resonant coupling for both crystalline and amorphous ice. By contrast, the insensitivity of isotropic scattering near 3420 cm/sup -1/ to isotopic dilution suggests that the overtone of the bending mode is the likely source.

• Research Organization: Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078
• OSTI ID: 6565568
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 90:3; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
AMORPHOUS STATE
DEUTERIUM
ENERGY LEVELS
EXCITED STATES
FILMS
HEAVY WATER
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
ICE
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
POLARIZATION
RAMAN SPECTRA
SPECTRA
STABLE ISOTOPES
THIN FILMS
VIBRATIONAL STATES
WATER