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Title: Vibrational spectroscopy of inorganic crystals and other materials.
Authors: Fernando, Waduge Sumanasiri.
Award date: 1972
Presented at: University of Leicester
Abstract: The vibrational spectra of five types of inorganic crystals and some powdered materials are presented and discussed on the basis of currently accepted theories. The general background relating to single crystal Raman spectra is outlined. Single crystal Raman spectra of halogen-bridged complexes e.g. CsNicl3 and RbNicl3 show the number of bands as predicted by the theory. The change of cations of the above complexes have little effect on the spectra. All observed bands were assigned to their symmetry species unambiguously. A Raman study of the oriented single crystals of M(CO)6 M = Cr, Mo and W is presented with particular emphasis on Mo(CO)6. The intensity pattern in the v(C-O) region can be interpreted well on the basis of the "oriented gas phase approximation". Effects of polar and non-polar solvents on v(C-O) stretching modes have been discussed. Raman and infrared spectra of ruthenocene at liquid nitrogen temperature were recorded. An assignment for all modes including inactive modes is given on the basis of solid-state splittings and solution data. A comparative study of six-membered inorganic ring systems of (PNCl2)3, [(Me)2Sio]3 and [(Me)2SiNH]3 shows a general trend of the internal vibrations with change of atomic type. Single crystal Raman data were used to confirm the four polarized modes of (PNCl2)3. The v4, 3(Cl-P-Cl) mode of (PNCl2)3 was observed in dichloromethane. An attempt was made to correlate the observed and calculated depolarization ratios of (PNCl2)3 in solution. Far-i.r. spectra of [(Me)2Sio]3 and [(Me)2SiNH]3 were recorded and an almost complete assignment was attempted. For [(Me)2SiNH]3 D3h symmetry is found adequate to explain the observed number of bands in i.r. and Raman spectra. Vibrational frequencies of norbornadiene (NBD), Cr(CO)4NBD and Cl2PdNBD are reported and a partial assignment is given. Metal-ligand vibrations are located on the basis of their polarization property and are found to be the lowest so far reported. The single crystal Raman spectra of the addtion compounds EI3.3S8 (E = Sb, As and CH) are tabulated and discussed in the light of "the oriented gas phase approximation" and correlation splittings. An attempt was made to confirm the symmetry species of the molecular modes of sulphur.
Type: Thesis
Level: Doctoral
Qualification: Ph.D.
Rights: Copyright © the author. All rights reserved.
Appears in Collections:Theses, Dept. of Chemistry
Leicester Theses

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