Vibration depolarized

Additional mfomiation about the vibration ean be obtained tln-ough the depolarization ratio. This is the ratio of the intensity of seattered light that is polarized in a plane perpendieular to the ineident radiation relative to that the seattered light that is polarized parallel to the ineident polarization, p For totally synnnetrie... 

The second ring vibration gives rise to a very weak infrared absorption band at 467 cm and to a weak and depolarized Raman line at 470 cm (202, 203) (Table 1-23). 

The frequencies classified in suites IX and X belong to depolarized Raman lines and correspond to vibrations-rotation bands of the C type. They can be assigned to oscillations of A" symmetry. 

The Raman spectrum can be used to give additional information regarding the symmetry properties of vibrations. This information derives from the measurement of the depolarization ratio p for each Raman band. The quantity p is a measure of the degree to which the polarization properties of the incident radiation may be changed after scattering... 

It is experimentally easy to generate Raman spectra using polarized light and to observe the partial depolarization of the spectra. Bands of totally symmetric vibrations are strongly polarized in Hquid or solution spectra. AH other bands in Hquid or solution are depolarized. Polarization effects are essential to elucidate stmctures, but are usuaHy ignored in most other appHcations. Details of the theory and experimental procedure can be found in the Hterature (15,16). 

Depolarization data on trimethylphosphine oxide are now available and the relationship between the symmetric and asymmetric POP vibrations has been equated for diphosphates, and some halogen and metal salt derivatives. The polarization of a carbonyl group produced by its conjugation with an ylide causes a large decrease in vco- This shift to lower frequency is increased further when a double bond is interposed, thus increasing the extent of conjugation. -... 

It is important from a practical viewpoint to predict the shear viscosity of mixtures from those of pure melts. For alkali nitrate melts, a linear dependence has been found between the reorientational line width obtained by Raman measurements and the ratio of temperature divided by shear viscosity.For NO3 ions, the depolarized Raman scattering from 1050cm" total stretching vibrational mode (Al) has a contribution to the line width L, which is caused by the reorientational relaxation time of the Csv axis of this ion. The Stokes-Einstein-Debye(SED) relation establishes a relation between the shear viscosity r of a melt and the relaxation time for the reorientation of a particle immersed in it ... 

Besides the vibrational frequency, symmetry is another important feature to describe a vibrational motion. The symmetry of a normal vibration can be determined by measuring the depolarization ration of the corresponding Raman band, which is defined as... 

An approach simpler than the "general" method has been used by Bower and coworkers [52,53] and has proved to be useful to determine the order parameters of uniaxially oriented polymers. This approach, called "cylindrical" method, requires a smaller number of spectra that are easily measurable, but it assumes that the Raman tensor associated with the vibrational mode under study is cylindrical. In such case, at — a2 — a so that the depolarization ratio R so of an... 

Lipari G. and Szabo A. (1980) Effect of Vibrational Motion on Fluorescence Depolarization and Nuclear Magnetic Resonance Relaxation in Macromolecules and Membranes, Biophys. J. 30, 489—506. Steiner R. F. (1991) Fluorescence Anisotropy Theory and Applications, in Lakowicz J. R. (Ed.), Topics in Fluorescence Spectroscopy, Vol. 2, Principles, Plenum Press, New York, pp. 127-176. 

Lipari G. and Szabo A. (1980) Effect of Vibrational Motion on Fluorescence Depolarization and Nuclear Magnetic Resonance Relaxation in Macromolecules and Membranes, Biophys. J. 30, 489-506. 

The carbonyl stretching frequency of both the keto and enol tautomers can be recognized in the vibrational spectrum of pentane-2,4-dione. The enol has v(C=0) at 1618cm" , generally the dominant peak in the spectrum and more intense than the in- and out-of-phase v(C=0) stretching modes of the keto form, which are found at 1727 and 1707 cm" , respectively. These are identified by their Raman counterparts at 1719 cm" (polarized) and 1697 cm" (depolarized) (Ernstbrunner, 1970). The ratio of absorbances of the enol and the out-of-phase keto bands in the ir was used as an early method of analysis of the keto/enol equilibrium in different solvents (Le Fevre and Welsh, 1949). 

Vibrational Raman Scattering of radiation with changed frequency due lo polarizability change during a vibration (A = visible usually) Qualitative for large molecules 10-Ms 10 Pa (100 ion) (v dependent) Useful for characterization. Some structural information from number of bands, position, depolarization ratios, and possibly Isotope effects. All... 

Theoretically, 0=s p =s 3/4, depending on the nature and symmetry of the vibration. Nonsymmetric vibrations give depolarizations of 3/4. Symmetric vibrations give p ranging from 0 to 3/4. Accurate values of p are important for determining the assignment of a Raman line to a symmetric or an asymmetric vibration. 

Measuring the depolarization ratio, therefore, provides a direct, spectroscopic determination of the structure and dynamics of vibrational modes. Furthermore, this experiment can be used to determine the parameter e, which must be known for quantitative measurements of the order parameters in oriented systems. 

Besides being always Raman active, the totally symmetric vibrational modes can also be readily identified in the spectrum. As shown in Fig. 7.3.2, the scattered Raman radiation can be resolved into two intensity components, /l and 7. The ratio of these two intensities is called the depolarization ratio p ... 

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