Theoretical investigations of the excited-state intramolecular proton transfer reaction in N-substituted-3-hydroxypyridinones

Andrzej L. Sobolewski, Ludwik Adamowicz

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The potential energy functions of the electronic ground state, as well as the lowest nπ* and ππ* excited singlet states of 3-hydroxy-4-pyridinone and 3-hydroxy-2-methyl-4-pyridinone, have been theoretically investigated along the proton transfer (PT) reaction coordinate. The full geometry optimization has been performed along the PT reaction path. In the geometry optimization, the Hartree-Fock approximation and the configuration interaction scheme with single excitations have been employed. The energy calculations at the optimized geometries have been performed with the complete-active space self-consistent field (CASSCF) method followed by second-order perturbation theory calculations, employing the CASSCF wave function as the reference. We found that the near-degeneracy between the ππ* and nπ* excited singlet states, which is removed upon methyl substitution, might be the factor which differentiates the two systems with respect to the excited state intramolecular PT reaction. A simple vibrational model has been proposed for investigation of the dynamics of the process.

Original languageEnglish (US)
Pages (from-to)67-78
Number of pages12
JournalChemical Physics
Volume193
Issue number1-2
DOIs
StatePublished - Apr 1 1995

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Proton transfer
Excited states
protons
Geometry
Hartree approximation
Potential energy functions
Pyridones
excitation
self consistent fields
geometry
Wave functions
Ground state
optimization
Substitution reactions
configuration interaction
perturbation theory
potential energy
wave functions
substitutes
ground state

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Physics and Astronomy(all)

Cite this

Theoretical investigations of the excited-state intramolecular proton transfer reaction in N-substituted-3-hydroxypyridinones. / Sobolewski, Andrzej L.; Adamowicz, Ludwik.

In: Chemical Physics, Vol. 193, No. 1-2, 01.04.1995, p. 67-78.

Research output: Contribution to journalArticle

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