The photoelectron spectroscopy of some transient diatomic molecules
The photoelectron spectroscopy of some transient diatomic molecules
The construction of a photoelectron spectrometer specifically designed for the study of transient species is described. An RF induction furnace for use inside the ionization chamber of the above spectrometer, and hence suitable for generating short-lived species in a suitable position to be examined by p.e.s. is also described. The furnace, capable of attaining temperatures up to 2000 K, may be used for either gaseous or solid precursors. This pyrolytic technique as well as gas phase atom-molecule reactions are used to generate the transient species studied.The transient species studied in this work are P (X' r.. +), PN(X'z ) and CIO (X2ni). The first i.p. of the P02(X2fir) molecule is also reported.The P2 (X's +) molecule is produced by the pyrolysis of P4 vapour. The gssociated PN (X't+) molecule is produced by pyrolysis of P3N5 and also by the reaction of P2 with NO on heated carbon. The observed photoelectron spectra are interpreted by analogy with the well known p.e. spectrum of N2 (X't +) and with the aid of ab initio molecular orbital calculations. The relative ordering of the first two ionic states in the P2 PN and N2 series are examined in terms of the corrections to Koopmans' theorem. Some preliminary investigations of the reactions of the P2 molecule are reported. This resulted in the observation of the PO molecule by p.e.s. for the first time.The CIO (2111) molecule is produced by the rapid gas phase atom molecule reactions between chlorine atoms and ozone, and chlorine atoms and chlorine dioxide, enabling several previously unidentified states of C10+ to be characterised. A theoretical prediction of the relative ordering of the six ionic states produced from ionization from the 2n orbital of C10 yields a different result from the prediction based on the extension of Hund's rules to linear molecules.
University of Southampton
1978
Bulgin, Denis Keith
(1978)
The photoelectron spectroscopy of some transient diatomic molecules.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The construction of a photoelectron spectrometer specifically designed for the study of transient species is described. An RF induction furnace for use inside the ionization chamber of the above spectrometer, and hence suitable for generating short-lived species in a suitable position to be examined by p.e.s. is also described. The furnace, capable of attaining temperatures up to 2000 K, may be used for either gaseous or solid precursors. This pyrolytic technique as well as gas phase atom-molecule reactions are used to generate the transient species studied.The transient species studied in this work are P (X' r.. +), PN(X'z ) and CIO (X2ni). The first i.p. of the P02(X2fir) molecule is also reported.The P2 (X's +) molecule is produced by the pyrolysis of P4 vapour. The gssociated PN (X't+) molecule is produced by pyrolysis of P3N5 and also by the reaction of P2 with NO on heated carbon. The observed photoelectron spectra are interpreted by analogy with the well known p.e. spectrum of N2 (X't +) and with the aid of ab initio molecular orbital calculations. The relative ordering of the first two ionic states in the P2 PN and N2 series are examined in terms of the corrections to Koopmans' theorem. Some preliminary investigations of the reactions of the P2 molecule are reported. This resulted in the observation of the PO molecule by p.e.s. for the first time.The CIO (2111) molecule is produced by the rapid gas phase atom molecule reactions between chlorine atoms and ozone, and chlorine atoms and chlorine dioxide, enabling several previously unidentified states of C10+ to be characterised. A theoretical prediction of the relative ordering of the six ionic states produced from ionization from the 2n orbital of C10 yields a different result from the prediction based on the extension of Hund's rules to linear molecules.
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Published date: 1978
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Local EPrints ID: 463459
URI: http://eprints.soton.ac.uk/id/eprint/463459
PURE UUID: 31d68f3f-3a9a-4593-b0df-2cfd9246c0d1
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Date deposited: 04 Jul 2022 20:52
Last modified: 04 Jul 2022 20:52
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Author:
Denis Keith Bulgin
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