We report a combined experimental and theoretical study of photoionization (PI) of the NO2 molecule into the NO2+ (X 1Σg+) ground state and the photodissociation of NO2 into the NO+(1Σ+) + O−(2P) ion pair. These processes were induced by 10.9 eV–13 eV synchrotron radiation and the products were detected using electron-ion or O−–NO+ coincident momentum spectroscopy. The results demonstrate the strong influence of [R*(4b2)−1, nlαi, |$v_2^\prime $|] Rydberg states vibrationally resolved in the |$v_2^\prime $| bending modes for both processes. In particular, we emphasize two regions around 11.5 eV and 12.5 eV that were studied in more detail for their relevance to 400 nm multiphoton ionization induced by femtosecond pulses. The photoelectron energy spectra and asymmetry parameters support the existence of two PI mechanisms, as probed with the help of fixed-nuclei frozen-core Hartree-Fock calculations. We found significant deviations from Franck-Condon ionization predictions which may be assigned to vibronic coupling of NO2* states such as that induced by a conical intersection. The limited agreement between theory and experiment, even for the non-resonant processes, indicates the need for calculations that go beyond the approximations used in the current study. Ion pair formation leads to strong vibrational and rotational excitation of the NO+(1Σ+,v) product, with an ion fragment angular anisotropy depending on both the |$v_2^\prime $| bending quantum number of the excited parent molecule and the v vibrational level of the fragment.
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28 July 2013
Research Article|
July 26 2013
The role of Rydberg states in photoionization of NO2 and (NO+, O−) ion pair formation induced by one VUV photon
S. Marggi Poullain;
S. Marggi Poullain
1Institut des Sciences Moléculaires d’Orsay (UMR 8214 Université Paris-Sud et CNRS), Bat. 210-350,
Université Paris Sud
, F-91405 Orsay Cedex, France
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K. Veyrinas;
K. Veyrinas
1Institut des Sciences Moléculaires d’Orsay (UMR 8214 Université Paris-Sud et CNRS), Bat. 210-350,
Université Paris Sud
, F-91405 Orsay Cedex, France
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P. Billaud;
P. Billaud
1Institut des Sciences Moléculaires d’Orsay (UMR 8214 Université Paris-Sud et CNRS), Bat. 210-350,
Université Paris Sud
, F-91405 Orsay Cedex, France
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M. Lebech;
M. Lebech
2
Niels Bohr Institute
, DK-2100 Copenhagen, Denmark
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Y. J. Picard;
Y. J. Picard
1Institut des Sciences Moléculaires d’Orsay (UMR 8214 Université Paris-Sud et CNRS), Bat. 210-350,
Université Paris Sud
, F-91405 Orsay Cedex, France
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R. R. Lucchese;
R. R. Lucchese
3Department of Chemistry,
Texas A&M University
, College Station, Texas 77843, USA
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D. Dowek
D. Dowek
1Institut des Sciences Moléculaires d’Orsay (UMR 8214 Université Paris-Sud et CNRS), Bat. 210-350,
Université Paris Sud
, F-91405 Orsay Cedex, France
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J. Chem. Phys. 139, 044311 (2013)
Article history
Received:
March 19 2013
Accepted:
June 07 2013
Citation
S. Marggi Poullain, K. Veyrinas, P. Billaud, M. Lebech, Y. J. Picard, R. R. Lucchese, D. Dowek; The role of Rydberg states in photoionization of NO2 and (NO+, O−) ion pair formation induced by one VUV photon. J. Chem. Phys. 28 July 2013; 139 (4): 044311. https://doi.org/10.1063/1.4811713
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