Multiple product pathways in photodissociation of nitromethane at 213 nm
- Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)
In this paper, we present a photodissociation dynamics study of nitromethane at 213 nm in the π → π{sup *} transition. Resonantly enhanced multiphoton ionization spectroscopy and ion-imaging were applied to measure the internal state distributions and state-resolved scattering distributions of the CH{sub 3}, NO(X {sup 2}Π, A {sup 2}Σ{sup +}), and O({sup 3}P{sub J}) photofragments. The rotationally state-resolved scattering distribution of the CH{sub 3} 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 CH{sub 3} fragment indicated the production of the NO{sub 2} counter-product in the electronic excited state, wherein 1 {sup 2}B{sub 2} 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({sup 3}P{sub J}) photofragment was found to be higher than the one-photon dissociation threshold, indicating the two-photon process involved. The NO(A {sup 2}Σ{sup +}) fragment, which was detected by ionization spectroscopy via the Rydberg ←A {sup 2}Σ{sup +} transition, also required two-photon energy. These experimental data corroborate the existence of competing photodissociation product pathways, CH{sub 3} + NO{sub 2},CH{sub 3} + NO + O,CH{sub 3}O + NO, and CH{sub 3}NO + O, following the π → π{sup *} 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.
- OSTI ID:
- 22493731
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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