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Mechanism of an Exceptional Class of photostabilizers: a seam of conical intersection parallel to excited state intramolecular proton transfer (ESIPT) in o-hydroxyphenyl-(1,3,5)-triazine.

Authors
  • Paterson, Martin J
  • Robb, Michael A
  • Blancafort, Lluís
  • DeBellis, Anthony D
Type
Published Article
Journal
The journal of physical chemistry. A
Publication Date
Aug 25, 2005
Volume
109
Issue
33
Pages
7527–7537
Identifiers
PMID: 16834122
Source
Medline
License
Unknown

Abstract

We present a detailed CASSCF study of the mechanism of excited-state intramolecular proton transfer (ESIPT) in the o-hydroxyphenyl triazine class of photostabilizers. The valence-bond analysis of the ground state and the two pipi* excited states permits a simple chemical interpretation of the mechanistic information. Our results show that the barrier to enol-keto tautomerism on the ground-state adiabatic surface is high. Following photoexcitation to the charge-transfer state, the ESIPT is predicted to take place without a barrier. Radiationless decay to the ground state is associated with an extended seam of conical intersection, with a sloped topology lying parallel to the ESIPT path, which can be accessed at any point along the reaction path. Our results show that the triazine class of photostabilizers has the photochemical and photophysical qualities associated with exceptional photostability.

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