Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Effects of Amino Substitution on the Excited State Hydrogen Transfer in Phenol: A TDDFT Study

  • Kim, Sang-Su (Department of Chemistry, Ajou University) ;
  • Kim, Min-Ho (Division of Energy Systems Research, Ajou University) ;
  • Kang, Hyuk (Department of Chemistry, Ajou University)
  • Published : 2009.07.20
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Abstract

When isolated phenol or a small phenol-solvent cluster is excited to the $S_1\;state\;of\;{\pi}{\pi}^*$ character, the hydrogen atom of the hydroxyl group dissociates via a ${\pi}{\sigma}^*$ state that is repulsive along the O-H bond. We computationally investigated the substitution effects of an amino group on the excited state hydrogen transfer reaction of phenol. The time-dependent density functional theory (TDDFT) with B3LYP functional was employed to calculate the potential energy profiles of the ${\pi}{\pi}^*$ and the ${\pi}{\sigma}^*$ excited states along the O-H coordinate, together with the orbital shape at each point, as the position of the substituent was varied. It was found that the amino substitution has an effect of lowering the ${\pi}{\sigma}^*$ state and enhancing the excited state hydrogen transfer reaction.

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