Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry

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Abstract

Dissociative double-photoionization of butadiene in the 25-45 eV energy range has been studied
with tunable synchrotron radiation using full three-dimensional ion momentum imaging. Using ab
initio calculations, the electronic states of the molecular dication below 33 eV are identified. The
results of the measurement and calculation show that double ionization from π orbitals selectively
triggers twisting about the terminal or central C–C bonds. We show that this conformational rearrangement
depends upon the dication electronic state, which effectively acts as a gateway for the
dissociation reaction pathway. For photon energies above 33 eV, three-body dissociation channels
where neutral H-atom evaporation precedes C–C charge-separation in the dication species appear in
the correlation map. The fragment angular distributions support a model where the dication species
is initially aligned with the molecular backbone parallel to the polarization vector of the light,
indicating a high probability for double-ionization to the “gateway states” for molecules with this orientation.

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  • Chemical Sciences
Original languageEnglish
Pages (from-to)114309-114309
JournalJournal of Chemical Physics
Volume143
Issue number11
Publication statusPublished - 2015
Publication categoryResearch
Peer-reviewedYes