We have measured the density of supercooled water (H2O) in the range −33.41≤T≤−5.23 °C. Our samples were held in glass capillary tubing with an approximate inside diameter of 0.3 mm=300 μ. These samples were prepared by Mossop’s method and could be cooled to their homogeneous nucleation limit before freezing. We compare our density data to other measurements using capillaries and demonstrate what appears to be an excess density in smaller capillaries which is inversely proportional to the capillary inside diameter. The origins of this excess density are unknown, but we show its effect is insignificant on our measurement. The thermal expansivities derived from our data are fit to a power law in temperature relative to a singular temperature. These results are inconclusive due to a poor knowledge of the background expansivity.

A method is described for obtaining ultrahigh time-resolution vibrational spectra of shocked polycrystalline materials. A microfabricated shock target array assembly is used, consisting of a polymer shock generation layer, a polymer buffer layer, and a thin sample layer. A near-IR pump pulse launches the shock. A pair of delayed visible probe pulses generate a coherent anti-Stokes Raman (CARS) spectrum of the sample. High-resolution Raman spectra of shocked crystalline anthracene are obtained. From the Raman shock shift, the shock pressure is determined to be 2.6 GPa. The rise time of shock loading is 400 ps. This rise time is limited by hydrodynamics of the shock generation layer. The shock velocity in the buffer layer is found to be 3.7 (±0.5) km/s, consistent with the observed shock pressure. As the shock propagates through a few μm of buffer material, the rise time and pressure can be monitored. The rise time decreases from ∼800 to ∼400 ps over the first 6 μm of travel, and the pressure begins to decline after about 12 μm of travel. The high-resolution CARS method permits detailed analysis of the vibrational line shape. Simulations of the CARS spectra show that when the shock front is in the crystal layer the spectral linewidths are inhomogeneously broadened by the distribution of pressures in the layers. When the crystal layer is behind the front, the spectral linewidth can be used to estimate the temperature. The increase of the spectral width from the ambient 4 to ∼6.5 cm−1 is consistent with the expected temperature increase of ∼200°.

Articles you may be interested inMolecular dynamics with quantum transitions study of the vibrational relaxation of the HOD bend fundamental in liquid D2O Polarized Raman spectra for the full range of isotopic dilution for ice Ic and amorphous ice: Mixtures of intact H2O and D2OWe present Raman data for the OD stretch mode of 10 mol % HOD in H 2 0 for the liquid phase from -31.5 to 160 ·C. We find that an exact isosbestic does not hold, but rather the crossing of isotherms slowly but uniformly changes with temperature. We present an analysis based on Boltzmann statistics which gives evidence for a distribution of deuterium hydrogen bond strengths with minimum energy near the frequency (2440 cm -I) also found in the solid ice and amorphous solid phases. This analysis also gives evidence for a band of frequencies above 2630 cm -I due to OD oscillators all at essentially the same high energy relative to the strongest hydrogen bonds, and we interpret this band as due to broken hydrogen bonds. This allows us to calculate hydrogen bond probabilities, and we find this probability increases with decreasing temperature and approaches a value equal to the four bonded percolation threshold near the singular temperature Ts"" -45 ·C for the anomalies of supercooled water. Peak frequency and full width at half-maximum of the OD stretch band are found to drop precipitously to the amorphous solid values as T -+ Ts implying the ultimate state of supercooled water is similar to the amorphous solid.6954

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We have studied the OH stretch spectrum in water to explore the effects of interoscillator coupling. Both H2O, which may have significant intra and intermolecular coupling, and dilute HOD in D2O, which is isotopically decoupled, were studied over a broad range of temperature from −33 °C to 160 °C. By adding a small amount of a calibration dopant, we obtained quantitative spectra. We found interoscillator coupling plays a large role at all temperatures. At high temperature, intramolecular coupling contributes to a downshift in the peak position for H2O as compared to HOD. Intermolecular coupling, however, still has some influence at high temperature. At low temperature, the large excess intensity below 3200 cm−1 in H2O compared to HOD we find is due to an enhanced Raman cross section due to intermolecularly coupled in-phase OH stretch oscillations. We define a degree of delocalization for coupling as the idealized number of perfectly in-phase oscillators that could cause the enhanced scattering and find N≂2 for liquid H2O at −33 °C. An exact isosbestic crossing is not found and this can be understood given the changing line shape that the intermolecular coupling can induce. All the properties of the spectrum approach those found in amorphous solid water or ice near the supercooled water anomalous temperature, Ts≂−45 °C.