The molecular structure of liquid water has been an outstanding issue for many years. The identification of free -OH holds the key in differentiating structure models for liquid water. By analyzing the relative changes of the intensity and depolarization ratio in temperature dependent Raman spectra, the occurrence of free -OH in liquid water is unambiguously de- termined. Furthermore, upon the increase of temperature from 5 ~C to 85 ~C, the structure of liquid water undergoes significant change, but the relative proportion of free -OH is con- siderably small and remains almost unchanged. This implies that the breaking of hydrogen bond from the tetrahedral structure prefers to The energetic favoring of the structural change experiments. occur at the site of the hydrogen acceptor. for liquid water is thus clearly revealed from
The structure difference between light and heavy liquid water has been systematically in- vestigated by high precision Raman spectroscopy over the temperature range of 5-85℃. Distinct difference between the Raman spectral profiles of two different liquid waters is clearly observed. By analyzing the temperature-dependent Raman spectral contour using global fitting procedure, it is found that the micro-structure of heavy water is more ordered than that of light water at the same temperature, and the structure difference between the light and heavy water decreases with the increase of the temperature. The temperature off- set, an indicator for the structure difference, is determined to vary from 28 ℃ to 18 ℃ for the low-to-high temperature. It indicates that quantum effect is significantly not only at low temperature, but also at room temperature. The interaction energy among water molecules has also been estimated from van't Hoff's relationship. The detailed structural information should help to develop reliable force fields for molecular modeling of liquid water.
The origin of the Rayleigh scattering ring effect has been experimentally examined on a quantum dot/metal film system, in which CdTe quantum dots embedded in PVP are spincoated on a thin Au film. On the basis of the angle-dependent, optical measurements under different excitation schemes (i.e., wavelength and polarization), we demonstrate that surface plasmon assisted directional radiation is responsible for such an effect. Moreover, an interesting phase-shift behavior is addressed.
Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate (SDS) in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.