Caveats in the interpretation of time-resolved photoionization measurements: A photoelectron imaging study of pyrrole

Stuart W. Crane, Magdalena M. Zawadzki, James Oliver Frank Thompson, Nikoleta Kotsina, Mohammed Omair Ghafur, David Townsend

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8 Citations (Scopus)
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Abstract

We report time-resolved photoelectron imaging studies of gas-phase pyrrole over the 267-240 nm excitation region, recorded in conjunction with a 300 nm probe. Of specific interest is the lowest-lying (3s/πσ) state, which exhibits very weak oscillator strength but is thought to be excited directly at wavelengths ≤254 nm. We conclude, however, that the only significant contribution to our photoelectron data at all wavelengths investigated is from non-resonant ionization. Our findings do not rule out (3s/πσ) state excitation (as appears to be confirmed by supporting time-resolved ion-yield measurements) but do potentially highlight important caveats regarding the use and interpretation of photoreactant ionization measurements to interrogate dynamical processes in systems exhibiting significant topological differences between the potential energy surfaces of the neutral and cation states.

Original languageEnglish
Article number234304
JournalJournal of Chemical Physics
Volume145
Issue number23
Early online date16 Dec 2016
DOIs
Publication statusPublished - 21 Dec 2016

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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