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Threshold photoelectron spectroscopy (TPES) of vibrationally excited nitrogen

Threshold photoelectron spectroscopy (TPES) of vibrationally excited nitrogen
Threshold photoelectron spectroscopy (TPES) of vibrationally excited nitrogen
Threshold photoelectron spectroscopy (TPES) has been used to study flowing nitrogen subjected to a microwave discharge. The first three photoelectron (PE) bands of nitrogen corresponding to the ionizations N2+ (X2?+g) v+ ? N2 (X1?+g) v'', N2+ (A2?u) v+ ? N2 (X1?+g) v'' and N2 + (B2?+u) v+ ? N2 (X1?+g) v'' were investigated. An analysis of the vibrationally resolved threshold photoelectron (TPE) spectra shows evidence of population of the vibrational levels v'' = 0–5 in the N2 X1?+g neutral state. By a comparison with the PE spectrum recorded under the same conditions, use of computed Franck–Condon factors for each ionization and evidence from vacuum ultraviolet absorption spectroscopy, the relative intensities of vibrational components in a TPE band can be qualitatively explained using the Franck–Condon factors for each ionization as well as the gain in intensity from autoionization from Rydberg states that are degenerate with an ionization threshold or lie just above a threshold. The enhancement in intensity obtained in the TPE spectra, relative to the intensity in a PE spectrum recorded under the same conditions, was estimated as at least one order of magnitude. The first band of atomic nitrogen was also observed in the discharge-on TPE spectra. The experimental resolution was sufficiently good to allow the three ionizations N+(3P0,1,2) ? N(4S3/2) to be resolved and their relative component intensities were measured as 1: 0.95 ± 0.10: 0.70 ± 0.10. The complementary nature of the TPES and PES techniques has been outlined and the extra information obtained from studying a vibrationally excited small molecule such as N2 with these methods has been demonstrated.
0953-4075
45002-45009
Innocenti, Fabrizio
2e95973e-c7b9-4166-8bf2-8b06a713fdfa
Eypper, Marie
de5d8ecd-5e65-4bc0-b3ce-91574700448d
Stranges, S.
c2fdbc8d-800a-4281-b093-e32d818388ca
West, J.B.
1ab6d458-abb8-41a0-b5e9-640ce811c2db
King, G.C.
1c4af097-2a64-4466-b9fd-079f923b4861
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Innocenti, Fabrizio
2e95973e-c7b9-4166-8bf2-8b06a713fdfa
Eypper, Marie
de5d8ecd-5e65-4bc0-b3ce-91574700448d
Stranges, S.
c2fdbc8d-800a-4281-b093-e32d818388ca
West, J.B.
1ab6d458-abb8-41a0-b5e9-640ce811c2db
King, G.C.
1c4af097-2a64-4466-b9fd-079f923b4861
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f

Innocenti, Fabrizio, Eypper, Marie, Stranges, S., West, J.B., King, G.C. and Dyke, John M. (2013) Threshold photoelectron spectroscopy (TPES) of vibrationally excited nitrogen. Journal of Physics B: Atomic and Molecular Physics, 46 (4), 45002-45009. (doi:10.1088/0953-4075/46/4/045002).

Record type: Article

Abstract

Threshold photoelectron spectroscopy (TPES) has been used to study flowing nitrogen subjected to a microwave discharge. The first three photoelectron (PE) bands of nitrogen corresponding to the ionizations N2+ (X2?+g) v+ ? N2 (X1?+g) v'', N2+ (A2?u) v+ ? N2 (X1?+g) v'' and N2 + (B2?+u) v+ ? N2 (X1?+g) v'' were investigated. An analysis of the vibrationally resolved threshold photoelectron (TPE) spectra shows evidence of population of the vibrational levels v'' = 0–5 in the N2 X1?+g neutral state. By a comparison with the PE spectrum recorded under the same conditions, use of computed Franck–Condon factors for each ionization and evidence from vacuum ultraviolet absorption spectroscopy, the relative intensities of vibrational components in a TPE band can be qualitatively explained using the Franck–Condon factors for each ionization as well as the gain in intensity from autoionization from Rydberg states that are degenerate with an ionization threshold or lie just above a threshold. The enhancement in intensity obtained in the TPE spectra, relative to the intensity in a PE spectrum recorded under the same conditions, was estimated as at least one order of magnitude. The first band of atomic nitrogen was also observed in the discharge-on TPE spectra. The experimental resolution was sufficiently good to allow the three ionizations N+(3P0,1,2) ? N(4S3/2) to be resolved and their relative component intensities were measured as 1: 0.95 ± 0.10: 0.70 ± 0.10. The complementary nature of the TPES and PES techniques has been outlined and the extra information obtained from studying a vibrationally excited small molecule such as N2 with these methods has been demonstrated.

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Published date: 4 February 2013
Organisations: Chemistry

Identifiers

Local EPrints ID: 351499
URI: http://eprints.soton.ac.uk/id/eprint/351499
ISSN: 0953-4075
PURE UUID: 409835fc-539e-49cd-9dc8-af78fa2a7dbd
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 23 Apr 2013 11:33
Last modified: 20 Jul 2019 01:27

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Contributors

Author: Fabrizio Innocenti
Author: Marie Eypper
Author: S. Stranges
Author: J.B. West
Author: G.C. King
Author: John M. Dyke ORCID iD

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