Two-photon excited state dynamics of dark valence, rydberg, and superexcited states in 1,3-butadiene

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DOIResolve DOI: http://doi.org/10.1021/jz402725u
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TypeArticle
Journal titleJournal of Physical Chemistry Letters
ISSN1948-7185
Volume5
Issue3
Pages560565; # of pages: 6
SubjectAutoionization; Conical intersection; One photon absorption; Subpicosecond time scale; Superexcited state; Time-resolved photoelectron spectroscopy; Two photon absorption; Butadiene; Decay (organic); Excited states; Mixing; Photoelectron spectroscopy; Photons; Rydberg states; Two photon processes; Dynamics
AbstractTwo-photon absorption in systems with parity permits access to states that cannot be prepared by one-photon absorption. Here we present the first time-resolved photoelectron spectroscopy study using this technique, applied to 1,3-butadiene, in which we investigated the dynamics of its dark valence, Rydberg, and superexcited states. The dark valence state dynamics are accessed via the Rydberg manifold, excited by two photons of 400 nm. We find that the 'dark' 21Ag state populated in this manner has a much longer lifetime than when accesses via the 11Bu 'bright' valence state when populated by one photon of 200 nm. In addition, we compared the dynamics of the 3sπ- and 3dπ-Rydberg states. These Rydberg states relax to the valence manifold on a subpicosecond time scale, with the 3sπ-Rydberg state decay rate being larger due to a stronger valence-Rydberg mixing. Finally, we investigated superexcited valence states that fragment or autoionize within 200 fs, likely without involving Rydberg states.
Publication date
PublisherACS Publications
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences; Security and Disruptive Technologies
Peer reviewedYes
NPARC number21272759
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Record identifiereea29a58-f58d-4ead-8935-0ac01bf7dbef
Record created2014-12-03
Record modified2016-05-09
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