Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols

Tolga N. V. Karsili, Andreas M. Wenge, Barbara Marchetti, Michael N. R. Ashfold*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

31 Citations (Scopus)
377 Downloads (Pure)

Abstract

We report a combined experimental (H (Rydberg) atom photofragment translational spectroscopy) and theoretical (ab initio electronic structure and vibronic coupling calculations) study of the effects of symmetry on the photodissociation dynamics of phenols. Ultraviolet photoexcitation to the bound S-1((1)(pi pi)*) state of many phenols leads to some O-H bond fission by tunneling through the barrier under the conical intersection (CI) between the S-1 and dissociative S-2(1(pi sigma)*) potential energy surfaces in the RO-H stretch coordinate. Careful analysis of the total kinetic energy release spectra of the resulting products shows that the radicals formed following S-1

Original languageEnglish
Pages (from-to)588-598
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume16
Issue number2
Early online date28 Oct 2013
DOIs
Publication statusPublished - 28 Oct 2014

Keywords

  • PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY
  • NEAR-UV PHOTOLYSIS
  • H-ATOM ELIMINATION
  • CONICAL INTERSECTIONS
  • ULTRAVIOLET PHOTOLYSIS
  • S-1 STATE
  • O-H
  • PYRROLE
  • MOLECULES
  • HYDROGEN

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