In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π* transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH3, NO(X 2Π, A 2Σ+), and O(3PJ) photofragments. The rotationally state-resolved scattering distribution of the CH3 fragment showed two velocity components, of which the slower one decreased the relative intensity as the rotational and vibrational excitations. The translational energy distribution of the faster CH3 fragment indicated the production of the NO2 counter-product in the electronic excited state, wherein 1 2B2 was the most probable. The NO(v = 0) fragment exhibited a bimodal translational energy distribution, whereas the NO(v = 1 and 2) fragment exhibited a single translational energy component with a relatively larger internal energy. The translational energy of a portion of the O(3PJ) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A 2Σ+) fragment, which was detected by ionization spectroscopy via the Rydberg ←A 2Σ+ transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH3 + NO2,CH3 + NO + O,CH3O + NO, and CH3NO + O, following the π → π* transition. The origins of the observed photofragments are discussed in this report along with recent theoretical studies and previous dynamics experiments performed at 193 nm.
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14 February 2016
Research Article|
February 08 2016
Multiple product pathways in photodissociation of nitromethane at 213 nm
Masataka Sumida;
Masataka Sumida
Department of Chemistry, Graduate School of Science,
Hiroshima University
, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526, Japan
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Yasunori Kohge;
Yasunori Kohge
Department of Chemistry, Graduate School of Science,
Hiroshima University
, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526, Japan
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Katsuyoshi Yamasaki;
Katsuyoshi Yamasaki
Department of Chemistry, Graduate School of Science,
Hiroshima University
, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526, Japan
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Hiroshi Kohguchi
Hiroshi Kohguchi
a)
Department of Chemistry, Graduate School of Science,
Hiroshima University
, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526, Japan
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 144, 064304 (2016)
Article history
Received:
November 11 2015
Accepted:
January 20 2016
Citation
Masataka Sumida, Yasunori Kohge, Katsuyoshi Yamasaki, Hiroshi Kohguchi; Multiple product pathways in photodissociation of nitromethane at 213 nm. J. Chem. Phys. 14 February 2016; 144 (6): 064304. https://doi.org/10.1063/1.4941090
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