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Characterisation of high temperature molecules by matrix isolation infrared spectroscopy and mass spectrometry

Characterisation of high temperature molecules by matrix isolation infrared spectroscopy and mass spectrometry
Characterisation of high temperature molecules by matrix isolation infrared spectroscopy and mass spectrometry

This thesis describes the use of matrix isolation infrared spectroscopy and mass spectrometry to characterise high temperature molecules of potential importance in a severe nuclear accident. Compounds of caesium, tellurium and ruthenium were studied due to their importance as fission products.

The vapour above tellurium dioxide was found to consist primarily of monomeric TeO2 with significant quantities of Te2O4. Infrared spectra of TeO2 were interpreted using a C2v structure, consistent with previous work. Tellurium isotope structure observed on both of the bond stretching modes has allowed the bond angle to be estimated at 105o. The infrared spectra of the dimer, Te2O4 were rationalised using a cyclic structure of either C2h or C2v point groups with two terminal oxygen atoms.

Molecular M2TeO3 (M = Cs, Rb or K) was identified in the vapour above alkali metal tellurites (M2TeO3). The infrared spectra of molecular M2TeO3 species were interpreted in terms of a pseudo-pyramidal TeO3 structure with one alkali metal atom co-ordinated to two oxygen atoms and the other to the unique oxygen atom.

The vapour above tellurium tetrachloride was found to contain predominantly molecular TeCl4. At higher vaporisation temperatures molecular TeCl2 was also identified. The vapour above a 1:1 mixture of tellurium: tellurium tetrachloride was found to consist mainly of molecular TeCl2. Infrared spectra of TeCl4 were interpreted in terms of a distorted trigonal bipyramidal structure with a vacant equatorial site, consistent with previous work. Infrared spectra of TeCl2 were interpreted in terms of a bent C2v structure.

The vapour above tellurium tetrabromide was found to consist mainly of molecular TeBr2 and Br2. The infrared spectra of TeBr2 were modelled using a bent C2v structure.

The vapour above the alkali metal ruthenates, M2RuO4 (M = Cs, Rb, K) were found to consist predominantly of molecular MRuO3.

University of Southampton
Day, Trevor Neil
Day, Trevor Neil

Day, Trevor Neil (1994) Characterisation of high temperature molecules by matrix isolation infrared spectroscopy and mass spectrometry. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

This thesis describes the use of matrix isolation infrared spectroscopy and mass spectrometry to characterise high temperature molecules of potential importance in a severe nuclear accident. Compounds of caesium, tellurium and ruthenium were studied due to their importance as fission products.

The vapour above tellurium dioxide was found to consist primarily of monomeric TeO2 with significant quantities of Te2O4. Infrared spectra of TeO2 were interpreted using a C2v structure, consistent with previous work. Tellurium isotope structure observed on both of the bond stretching modes has allowed the bond angle to be estimated at 105o. The infrared spectra of the dimer, Te2O4 were rationalised using a cyclic structure of either C2h or C2v point groups with two terminal oxygen atoms.

Molecular M2TeO3 (M = Cs, Rb or K) was identified in the vapour above alkali metal tellurites (M2TeO3). The infrared spectra of molecular M2TeO3 species were interpreted in terms of a pseudo-pyramidal TeO3 structure with one alkali metal atom co-ordinated to two oxygen atoms and the other to the unique oxygen atom.

The vapour above tellurium tetrachloride was found to contain predominantly molecular TeCl4. At higher vaporisation temperatures molecular TeCl2 was also identified. The vapour above a 1:1 mixture of tellurium: tellurium tetrachloride was found to consist mainly of molecular TeCl2. Infrared spectra of TeCl4 were interpreted in terms of a distorted trigonal bipyramidal structure with a vacant equatorial site, consistent with previous work. Infrared spectra of TeCl2 were interpreted in terms of a bent C2v structure.

The vapour above tellurium tetrabromide was found to consist mainly of molecular TeBr2 and Br2. The infrared spectra of TeBr2 were modelled using a bent C2v structure.

The vapour above the alkali metal ruthenates, M2RuO4 (M = Cs, Rb, K) were found to consist predominantly of molecular MRuO3.

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Published date: 1994

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Local EPrints ID: 458436
URI: http://eprints.soton.ac.uk/id/eprint/458436
PURE UUID: 226dc088-97e3-48e7-934c-461172d6ed4a

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Date deposited: 04 Jul 2022 16:49
Last modified: 04 Jul 2022 16:49

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Author: Trevor Neil Day

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