Effects of equilibrium H-bond distance and angle changes on Raman intensities from water.

The H-bond energy dispersion over the inhomogeneously broadened OD stretching contour from dilute HDO in H(2)O was determined from absolute Raman intensities; it displays a large minimum near omega=2440 cm(-1) from short, strong H bonds (in agreement with the peak omega from lda ice) and a large maximum near 2650-2675 cm(-1) due to extremely weak or broken H bonds (in agreement with the peak omega from dense, supercritical HDO in H(2)O, 0.9 g/cm(3), 673 K). The difference between extrema is the maximum H-bond DeltaE, 5100+/-500 cal/mol, in excellent agreement with Pauling's limiting value. A pressure of 1500 bars yields an additional maximum and shoulder between the two dispersion extrema from pure water; saturated NaCl in water shows the additional maximum. The maxima near 3350 cm(-1) (1500 bar) or near 3360 cm(-1) (NaCl-H(2)O) arise from bent H bonds; 3350 cm(-1) (1500 bar) corresponding to an angle of approximately 170 degrees in the joint frequency/bend, probability of Lawrence and Skinner. Rising omega refers to a higher probability of larger O-O distances, bent H bonds, and H-bond weakening and breakage. A approximately 50-80 cm(-1) difference between the 2727 cm(-1) OD peak from HDO in steam, and the 2650-2675 cm(-1) dispersion maximum is explained via the very broad approximately 60 cm(-1) liquid peak observed at 342 degrees C and 2000 bar.

Measurement of an isosbestic point in the Raman spectrum of liquid water by use of a backscattering geometry.

Measurements presented here confirm that a temperature-insensitive point occurs in the backscattered Raman spectrum from liquid water. This result, coupled with existing laboratory measurements of Raman scattering from liquid droplets, indicates that a Raman lidar measurement of cloud liquid water is feasible.

Raman spectral evidence for hydration forces between collagen triple helices.

Hydration forces are thought to result from the energetic cost of water rearrangement near macromolecular surfaces. Raman spectra, collected on the same collagen samples on which these forces were measured, reveal a continuous change in water hydrogen-bonding structure as a function of separation between collagen triple helices. The varying spectral parameters track the force-distance curve. The energetic cost of water "restructuring," estimated from the spectra, is consistent with the measured energy of intermolecular interaction. These correlations support the idea that the change in water structure underlies the exponentially varying forces seen in this system at least over the 13-18-A range of interaxial separations.