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Title: Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}

Abstract

The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO{sup +} was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO{sup +} were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X{sup +} {sup 3}Σ{sup −} ground state was determined to be 11.76 ± 0.02 eV, while for the a{sup +1}Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations.

Authors:
; ;  [1];  [2]; ; ;  [3];  [4]
  1. Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany)
  2. Synchrotron SOLEIL, l’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France)
  3. Laboratoire de Chimie-Physique, UMR 8000 CNRS and Université Paris-Sud 11, F-91405 Orsay Cedex (France)
  4. Molecular Dynamics Group, Paul Scherrer Institute (PSI), CH-5232 Villigen (Switzerland)
Publication Date:
OSTI Identifier:
22415769
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 18; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHLORINE; COMPUTERIZED SIMULATION; EV RANGE; EXCITED STATES; EXHAUST GASES; FRANCK-CONDON PRINCIPLE; GROUND STATES; ISOCYANATES; NITROGEN OXIDES; PHOTOELECTRON SPECTROSCOPY; PYROLYSIS; RADICALS; RESOLUTION; SYNCHROTRON RADIATION; ULTRAVIOLET RADIATION

Citation Formats

Holzmeier, Fabian, Lang, Melanie, Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de, Tang, Xiaofeng, Cunha de Miranda, Barbara, Romanzin, Claire, Alcaraz, Christian, and Hemberger, Patrick. Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}. United States: N. p., 2015. Web. doi:10.1063/1.4920951.
Holzmeier, Fabian, Lang, Melanie, Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de, Tang, Xiaofeng, Cunha de Miranda, Barbara, Romanzin, Claire, Alcaraz, Christian, & Hemberger, Patrick. Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}. United States. doi:10.1063/1.4920951.
Holzmeier, Fabian, Lang, Melanie, Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de, Tang, Xiaofeng, Cunha de Miranda, Barbara, Romanzin, Claire, Alcaraz, Christian, and Hemberger, Patrick. Thu . "Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}". United States. doi:10.1063/1.4920951.
@article{osti_22415769,
title = {Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO{sup +} and vibrational resolution in NCO{sup +}},
author = {Holzmeier, Fabian and Lang, Melanie and Fischer, Ingo, E-mail: ingo.fischer@uni-wuerzburg.de and Tang, Xiaofeng and Cunha de Miranda, Barbara and Romanzin, Claire and Alcaraz, Christian and Hemberger, Patrick},
abstractNote = {The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO{sup +} was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO{sup +} were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X{sup +} {sup 3}Σ{sup −} ground state was determined to be 11.76 ± 0.02 eV, while for the a{sup +1}Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations.},
doi = {10.1063/1.4920951},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}