Matrix isolation studies on some high temperature systems
Matrix isolation studies on some high temperature systems
This thesis describes the characterisation of a number of transition metal and lanthanide chloride molecules and some simple mixed oxide species of germanium and silicon using matrix isolation vibrational spectroscopy. A discussion of the matrix isolation experiment and other physical methods which may be used to study high temperature vapours is given. The analysis of matrix isolation vibrational spectra is outlined and the use of isotopic substitution to determine structural parameters for simple molecules is described. In particular the matrix isolation spectra of the vapours above mixtures of germanium and silicon oxides showed features which could only be assigned to mixed oxide species of the two metals. Variation in the experimental conditions led to the identification of vibrational frequencies of several new species, for which simple ring structures were proposed. Matrices containing the vapours from metal trichloride samples often contain a variety of species in addition to the simple MC1 (M = metal) species. Spectral features due to these other species often hinder the identification of monomer frequencies and the assignment of MC13 geometry. A thorough survey of MF2, MC12, MF3 and MC13 matrix frequency and structural data is followed by a discussion of experimental methods used to aid the assignment of MC13 geometry from the matrix spectra. Theoretical methods for predicting MX3 and MX2 (X = F, Cl) geometries are described and lead to the results of a series of extended Huckel molecular orbital calculations. Subsequent chapters describe original experimental work which result in the assignment of planar MC13 and linear MC12 geometries in most cases. However, an accurate bond angle determination was possible for the bent C2v YbCl molecule and the possibility of a pyramidal 0v geometry for LaCtt3 is discussed. The use of nitrogen matrices was found to result in the formation of new species not present in the corresponding argon matrices.
University of Southampton
1982
Wyatt, Robert Stephen
(1982)
Matrix isolation studies on some high temperature systems.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
This thesis describes the characterisation of a number of transition metal and lanthanide chloride molecules and some simple mixed oxide species of germanium and silicon using matrix isolation vibrational spectroscopy. A discussion of the matrix isolation experiment and other physical methods which may be used to study high temperature vapours is given. The analysis of matrix isolation vibrational spectra is outlined and the use of isotopic substitution to determine structural parameters for simple molecules is described. In particular the matrix isolation spectra of the vapours above mixtures of germanium and silicon oxides showed features which could only be assigned to mixed oxide species of the two metals. Variation in the experimental conditions led to the identification of vibrational frequencies of several new species, for which simple ring structures were proposed. Matrices containing the vapours from metal trichloride samples often contain a variety of species in addition to the simple MC1 (M = metal) species. Spectral features due to these other species often hinder the identification of monomer frequencies and the assignment of MC13 geometry. A thorough survey of MF2, MC12, MF3 and MC13 matrix frequency and structural data is followed by a discussion of experimental methods used to aid the assignment of MC13 geometry from the matrix spectra. Theoretical methods for predicting MX3 and MX2 (X = F, Cl) geometries are described and lead to the results of a series of extended Huckel molecular orbital calculations. Subsequent chapters describe original experimental work which result in the assignment of planar MC13 and linear MC12 geometries in most cases. However, an accurate bond angle determination was possible for the bent C2v YbCl molecule and the possibility of a pyramidal 0v geometry for LaCtt3 is discussed. The use of nitrogen matrices was found to result in the formation of new species not present in the corresponding argon matrices.
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Published date: 1982
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Local EPrints ID: 460101
URI: http://eprints.soton.ac.uk/id/eprint/460101
PURE UUID: f9bfab34-a29a-4c87-8374-bae6210e8a99
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Date deposited: 04 Jul 2022 17:52
Last modified: 04 Jul 2022 17:52
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Author:
Robert Stephen Wyatt
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