Quantum dynamics study of the excited-state double-proton transfer in 2,2′-bipyridyl-3,3′-diol

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Abstract

Density functional theory and quantum dynamics simulations have been used to study the double-proton transfer reaction in 2,2́-bipyridyl-3,3́- diol in the first singlet excited electronic state. This process is experimentally known to be branched: It consists of a fast, concerted reaction mechanism (τ ≈ 100 fs) and a stepwise reaction mechanism [with a fast initial step (τ ≈ 100 fs) and a slower final step (τ ≈ 10ps)]. Quantum dynamics simulations on a two-dimensional model reveal that the concerted reaction occurs despite the nonexistence of a concerted reaction path, but they fail to explain the relative slowness of the stepwise mechanism. A qualitative simulation using a three-dimensional model suggests that internal vibrational relaxation (IVR) might be the reason why the second stage of the stepwise mechanism is so slow.
Original languageEnglish
Pages (from-to)1372-1378
JournalChemPhysChem
Volume5
Issue number9
DOIs
Publication statusPublished - 20 Sep 2004

Keywords

  • Excited states
  • Femtochemistry
  • Proton transfer
  • Quantum dynamics
  • Reaction mechanisms

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