Millimetrewave and infrared studies of free radicals
Millimetrewave and infrared studies of free radicals
Two electron paramagnetic resonance spectrometers are described, operating in the millimetre wave ('u2.8 cm 1) and infrared (ti1800 cm 1) regions. Both spectrometers have been used to observe new spectra and hence obtain new or improved molecular parameters of transient free radicals. The millimetre wave spectrometer has been used to study Zeeman components of the J - 3 +- 2 rotational transition of selenium monoxide (SeO) in its x3E- ground state. The observed transitions near 85 GHz are analysed together with the other available data to obtain values for the main molecular parameters to microwave precision. The parameters obtained are of interest because they show a slight tendency toward Hund's case 'c' coupling in SeO; the anomalies can be rationalised by considering third-order perturbation contributions to the effective Hamiltonian.The infrared spectrometer uses a carbon monoxide laser as the radiation source. Vibration-rotation transitions of the formyl radical (HCO) have been studied near 1870 curl. The analysis of this infrared lint spectrum of HCO, which is far from trivial, is described in some detail. The parameters obtained for the excited vibrational level are very much as expected from simple structural considerations.In an appendix, the 611 infrared lmr spectrum of nitrogen monoxide (NO) is summarised, including a number of transitions which have not previously been reported.
University of Southampton
1980
Dumper, Keith
(1980)
Millimetrewave and infrared studies of free radicals.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Two electron paramagnetic resonance spectrometers are described, operating in the millimetre wave ('u2.8 cm 1) and infrared (ti1800 cm 1) regions. Both spectrometers have been used to observe new spectra and hence obtain new or improved molecular parameters of transient free radicals. The millimetre wave spectrometer has been used to study Zeeman components of the J - 3 +- 2 rotational transition of selenium monoxide (SeO) in its x3E- ground state. The observed transitions near 85 GHz are analysed together with the other available data to obtain values for the main molecular parameters to microwave precision. The parameters obtained are of interest because they show a slight tendency toward Hund's case 'c' coupling in SeO; the anomalies can be rationalised by considering third-order perturbation contributions to the effective Hamiltonian.The infrared spectrometer uses a carbon monoxide laser as the radiation source. Vibration-rotation transitions of the formyl radical (HCO) have been studied near 1870 curl. The analysis of this infrared lint spectrum of HCO, which is far from trivial, is described in some detail. The parameters obtained for the excited vibrational level are very much as expected from simple structural considerations.In an appendix, the 611 infrared lmr spectrum of nitrogen monoxide (NO) is summarised, including a number of transitions which have not previously been reported.
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Published date: 1980
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Local EPrints ID: 462757
URI: http://eprints.soton.ac.uk/id/eprint/462757
PURE UUID: dc119488-1b34-4f8c-a251-1b16355ae787
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Date deposited: 04 Jul 2022 19:51
Last modified: 04 Jul 2022 19:51
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Author:
Keith Dumper
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