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Dynamics in higher lying excited states: Valence to Rydberg transitions in the relaxation paths of pyrrole and methylated derivatives
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
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Number of Authors: 5
2017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 146, no 14, 144307Article in journal (Refereed) Published
Abstract [en]

The involvement of intermediate Rydberg states in the relaxation dynamics of small organic molecules which, after excitation to the valence manifold, also return to the valence manifold is rarely observed. We report here that such a transiently populated Rydberg state may offer the possibility to modify the outcome of a photochemical reaction. In a time resolved photoelectron study on pyrrole and its methylated derivatives, N-methyl pyrrole and 2,5-dimethyl pyrrole, 6.2 eV photons (200 nm) are used to excite these molecules into a bright pi pi* state. In each case, a pi 3p-Rydberg state, either the B-1(pi 3p(y)) or the A(2)(pi 3p(z)) state, is populated within 20-50 fs after excitation. The wavepacket then proceeds to the lower lying A(2)(pi sigma*) state within a further 20 fs, at which point two competing reaction channels can be accessed: prompt N-H (N-CH3) bond cleavage or return to the ground state via a conical intersection accessed after ring puckering, the latter of which is predicted to require an additional 100-160 fs depending on the molecule.

Place, publisher, year, edition, pages
2017. Vol. 146, no 14, 144307
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-143588DOI: 10.1063/1.4979681ISI: 000399078700017OAI: oai:DiVA.org:su-143588DiVA: diva2:1104099
Available from: 2017-05-31 Created: 2017-05-31 Last updated: 2017-05-31Bibliographically approved

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CiteExportLink to record
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Citation style
  • apa
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