Some studies in gas-phase photoelectron and chemielectron spectroscopy
Some studies in gas-phase photoelectron and chemielectron spectroscopy
The work presented in this thesis is concerned with the study of some small molecules by ultraviolet photoelectron spectroscopy and chemielectron spectroscopy. Although photoelectron studies of short-lived molecules generated by both rapid atom-molecule reactions and high temperature pyrolysis are presented, the majority of the work is concerned with the study of some metal oxidation chemiionization reactions by high temperature chemielectron spectroscopy. A description of the experimental techniques used are given together with a discussion of the problems encountered in attempting to record electron spectra at high temperatures and the methods used to overcome them. Those theoretical methods which have been used to assist in the assignment of the photoelectron spectra are also discussed. The HeI photoelectron spectra of the radicals CH33CHF and FCH2CHF, generated by suitable fluorine atom-molecule reactions are presented. The assignment of these spectra has been partly accomplished by performing ab-initio Hartree-Fock molecular orbital calculations on the neutral ground states of these molecules and their lowest-lying cationic states at the respective computed minimum energy geometries to obtain adiabatic and vertical first ionization energies at both the SCF and SCF+ CI levels. The HeI photoelectron spectrum of SiS, prepared by high temperature pyrolysis, has been recorded and the assignment of the observed photoelectron bands has been accomplished by means of configuration interaction molecular orbital calculations. This molecule represents an example of the breakdown in the one-electron ionization model. A theoretical study of the electronic structure of the alkali metal monoxides LiO and NaO and their low-lying ionic states is reported. Adiabatic and vertical ionization energies have been calculated together with equilibrium bond lengths, vibrational frequencies and dissociation energies for all of the neutral and ionic states considered. A large number of chemiionization reactions involving members of the lanthanide series of metals and PROB*LEM, O2(a1Deltag) and O(3P) have been investigated using chemielectron spectroscopy and chemiion mass spectrometry. These studies have been shown to reveal important reaction dynamical information as well as spectroscopic data relating to the product ions.
University of Southampton
Cockett, Martin Charles Roy
1989
Cockett, Martin Charles Roy
Cockett, Martin Charles Roy
(1989)
Some studies in gas-phase photoelectron and chemielectron spectroscopy.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The work presented in this thesis is concerned with the study of some small molecules by ultraviolet photoelectron spectroscopy and chemielectron spectroscopy. Although photoelectron studies of short-lived molecules generated by both rapid atom-molecule reactions and high temperature pyrolysis are presented, the majority of the work is concerned with the study of some metal oxidation chemiionization reactions by high temperature chemielectron spectroscopy. A description of the experimental techniques used are given together with a discussion of the problems encountered in attempting to record electron spectra at high temperatures and the methods used to overcome them. Those theoretical methods which have been used to assist in the assignment of the photoelectron spectra are also discussed. The HeI photoelectron spectra of the radicals CH33CHF and FCH2CHF, generated by suitable fluorine atom-molecule reactions are presented. The assignment of these spectra has been partly accomplished by performing ab-initio Hartree-Fock molecular orbital calculations on the neutral ground states of these molecules and their lowest-lying cationic states at the respective computed minimum energy geometries to obtain adiabatic and vertical first ionization energies at both the SCF and SCF+ CI levels. The HeI photoelectron spectrum of SiS, prepared by high temperature pyrolysis, has been recorded and the assignment of the observed photoelectron bands has been accomplished by means of configuration interaction molecular orbital calculations. This molecule represents an example of the breakdown in the one-electron ionization model. A theoretical study of the electronic structure of the alkali metal monoxides LiO and NaO and their low-lying ionic states is reported. Adiabatic and vertical ionization energies have been calculated together with equilibrium bond lengths, vibrational frequencies and dissociation energies for all of the neutral and ionic states considered. A large number of chemiionization reactions involving members of the lanthanide series of metals and PROB*LEM, O2(a1Deltag) and O(3P) have been investigated using chemielectron spectroscopy and chemiion mass spectrometry. These studies have been shown to reveal important reaction dynamical information as well as spectroscopic data relating to the product ions.
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Published date: 1989
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Local EPrints ID: 461621
URI: http://eprints.soton.ac.uk/id/eprint/461621
PURE UUID: 0d043050-42d3-4ee8-948e-78a98cac6a7c
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Date deposited: 04 Jul 2022 18:51
Last modified: 04 Jul 2022 18:51
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Author:
Martin Charles Roy Cockett
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