Direct Observation of Hydrogen Tunneling Dynamics in Photoexcited Phenol

Gareth M. Roberts, Adam S. Chatterley, Jamie D. Young, Vasilios G. Stavros*

*Corresponding author for this work

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

106 Citations (Scopus)

Abstract

The excited-state dynamics of phenol following ultraviolet (UV) irradiation have received considerable interest in recent years, most notably because they can provide a model for understanding the UV-induced dynamics of the aromatic amino acid tyrosine. Despite this, there has been some debate as to whether hydrogen tunneling dynamics play a significant role in phenol's excited-state O-H bond fission when UV excitation occurs below the (1)pi pi*/(1)pi sigma* conical intersection (CI). In this Letter, we present direct evidence that (1)pi sigma*-mediated O-H bond fission below the (1)pi pi*/(1)pi sigma* CI proceeds exclusively through hydrogen tunneling dynamics. The observation of hydrogen tunneling may have some parallels with proton tunneling dynamics from tyrosine residues (along the O-H bond of the phenol moiety) in a wide range of natural enzymes, potentially adding further justification for utilizing phenols as model systems for investigating tyrosine-based dynamics.

Original languageEnglish
Pages (from-to)348-352
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume3
Issue number3
DOIs
Publication statusPublished - 2 Feb 2012

Keywords

  • PHOTODISSOCIATION DYNAMICS
  • CONICAL INTERSECTIONS
  • ELECTRON
  • STATES
  • SPECTROSCOPY
  • BIOLOGY

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