Molecular rotational motions are known to influence both Raman scattering of light and nuclear spin relaxation. Therefore, the application of Raman bandshape analysis and NMR relaxation time measurements to probe molecular dynamics in liquids will provide us with a deeper understanding of the dynamical behavior and structure of molecules in the liquid phase. Presented here are (i) studies of molecular reorientation of acetonitrile in the neat liquid phase and in solution by Raman bandshape analysis and NMR relaxation; (ii) studies of reorientational dynamics and internal rotation in transition metal clusters by NMR relaxation.

Raman vibrational bands are sensitive to fluctuations in the molecular environment. Variations in the bandwidth and peak position can then be utilized to monitor molecular forces and interactions present in condense phases. Nuclear Magnetic Resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids since nuclear spin relaxation times are dependent on the details of molecular motion. Presented here is the solvent study of the Raman bandwidths and frequency displacements of the mode of the compounds CH3MCI3 (M = C, Si, Ge, Sn) in a number of solvents of widely varying molecular structure. Also, a detailed isotope dilution study of the modes in CH2CI2/CD2CI2 mixtures is presented. In this set of experiments, I observed broadening of the v1 mode of CH2C12 upon dilution,which is the first experimental observation of such behavior. The temperature-dependent carbon-13 relaxation times and nuclear Overhauser enhancements in neat dichloromethane were measured. In this study we found that the molecular reorientation of this molecule was highly anisotropic, but could be well characterized assuming quasi-symmetric top behavior. In addition, in order to gain a more complete understanding of the reorientational dynamics in dichloromethane, we analyzed the 13-C NMR relaxation of CH2CI2 both in "inert" solvents of differing viscosities and in interactive solvents of varying Lewis basicities. Various theoretical models were also applied in order to characterize dichloromethane1s reorientational dynamics.

The laser-induced molecular reorientation effect of guest-host dye-doped liquid crystals in isotropic phase has been studied by measuring the signals of optical Kerr effect using pulsed frequency-doubling Nd:YAG laser as a pumping source. The critical behavior near the isotropic-nematic transition has been observed when the temperature approaches to the phase transition of liquid crystal. The relaxation time constant is about several hundreds of ns as the temperature is far above the clearing point of liquid crystals and that is longer than 1500 ns as the temperature is close to the clearing point of liquid crystals. According to Landau¡¦s second phase transition theory, the interaction between liquid crystal molecules will be increased and the nonlinearity effect of liquid crystal will be enhanced when the temperature is near the clearing point of liquid crystal. The relaxation time constant of molecular reorientation is a function of viscosity and temperature of liquid crystal, the relationship can be fitted as£b0*exp(f/T)*(1/T-T*),where £b0 is the viscosity coefficient and T* is the clearing point of the sample. The optical Kerr signal is found to be proportional to the energy density of pumping source. The optical Kerr signal can be sustained as long as 20£gs when the energy density of pumping source reaches to 1J/cm sq. The enhancement of molecular reorientation effect is also observed by increasing the concentration of dye.

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