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Raman investigation of the temperature dependence of the bending v/sub 2/ and combination v/sub 2/ + v/sub L/ bands from liquid water

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100320a010· OSTI ID:7143940
; ;

Raman spectra were obtained from liquid water between 3 and 95/sup 0/C under absolute intensity conditions. Depolarized v/sub 2/ peak frequencies were observed to lie above the polarized peak values by 5-8 cm/sup -1/. Gaussian analysis indicated a narrow v/sub 2/ component centered approx. = 30-45 cm/sup -1/ above a broad v/sub 2/ component. The intensity of the sharp v/sub 2/ Gaussian component increased relative to the broad v/sub 2/ Gaussian component with increasing temperature. In addition, the depolarized X(ZX)Y total v/sub 2/ contour intensity was observed to increase with temperature rise, but the corresponding polarized X(ZZ)Y v/sub 2/ intensity was observed to decrease. Isosbestic points were observed in the v/sub 2/ + v/sub L/ (L = libration) combination band at 2060 cm/sup -1/, X(ZX)Y, and 2025 cm/sup -1/, X(ZZ)Y. Gaussian contour analysis revealed three components, at (1) 2050, (2) 2150, and (3) 2300 cm/sup -1/ (weak). A plot of the integrated component intensities 1n (I/sub 2/ + I/sub 3/)/I/sub 1/) versus 1/T yielded a characteristic enthalpy value of -2.5 +/- 0.1 kcal/mol of O-H ... O. The v/sub 2/ data indicated that the bending contour contains two unresolved components from fully hydrogen-bonded (4-HB) and from partially hydrogen-bonded (3-HB) structures. These bends are coupled to the corresponding 4-HB and 3-HB librations. One of the 3-HB librations occurs near approx. = 450 cm/sup -1/, and it plus the 3-HB bend gives rise to the 2050-cm/sup -1/ combination component, whose temperature dependence relative to the 4-HB components yields the present enthalpy value for hydrogen bond rupture. These results are compatible with the bifurcated hydrogen bond model of Giguere.

Research Organization:
Howard Univ., Washington, DC (USA)
OSTI ID:
7143940
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:9; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL BONDS
DATA
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
INFORMATION
LASER SPECTROSCOPY
MEDIUM TEMPERATURE
NUMERICAL DATA
OXYGEN COMPOUNDS
RAMAN SPECTRA
RAMAN SPECTROSCOPY
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE
VIBRATIONAL STATES
WATER