An ab initio study of the potential energy surface in the S1 state of 2-hydroxypyridine

Andrzej L. Sobolewski, Ludwik Adamowicz

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2(1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S1 state performed at the CIS/6-31G(d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the "mobile" hydrogen atom on the S1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a "direct" proton transfer reaction on the S1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.

Original languageEnglish (US)
Pages (from-to)193-201
Number of pages9
JournalChemical Physics
Volume213
Issue number1-3
StatePublished - Dec 15 1996

Fingerprint

Potential energy surfaces
potential energy
saddle points
Excited states
dissociation
Pyridones
Commonwealth of Independent States
Proton transfer
excitation
Hydrogen
hydrogen atoms
Association reactions
Atoms
Molecules
optimization
protons
Geometry
geometry
2-hydroxypyridine
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

An ab initio study of the potential energy surface in the S1 state of 2-hydroxypyridine. / Sobolewski, Andrzej L.; Adamowicz, Ludwik.

In: Chemical Physics, Vol. 213, No. 1-3, 15.12.1996, p. 193-201.

Research output: Contribution to journalArticle

@article{6d794b0b892349d7baea2cc02831a74f,
title = "An ab initio study of the potential energy surface in the S1 state of 2-hydroxypyridine",
abstract = "The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2(1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S1 state performed at the CIS/6-31G(d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the {"}mobile{"} hydrogen atom on the S1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a {"}direct{"} proton transfer reaction on the S1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.",
author = "Sobolewski, {Andrzej L.} and Ludwik Adamowicz",
year = "1996",
month = "12",
day = "15",
language = "English (US)",
volume = "213",
pages = "193--201",
journal = "Chemical Physics",
issn = "0301-0104",
publisher = "Elsevier",
number = "1-3",

}

TY - JOUR

T1 - An ab initio study of the potential energy surface in the S1 state of 2-hydroxypyridine

AU - Sobolewski, Andrzej L.

AU - Adamowicz, Ludwik

PY - 1996/12/15

Y1 - 1996/12/15

N2 - The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2(1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S1 state performed at the CIS/6-31G(d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the "mobile" hydrogen atom on the S1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a "direct" proton transfer reaction on the S1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.

AB - The potential energy (PE) surface of the lowest excited singlet state relevant to the photophysics of interconversion of the 2-hydroxypyridine/2(1H)-pyridinone (2HP/2PY) system is characterized by ab initio calculations. The geometry optimizations in the S1 state performed at the CIS/6-31G(d,p) level confirm the experimental findings that the 2HP form is planar in this state whereas the 2PY form is significantly out-of-plane distorted. The lowest-energy first-order saddle-points which are relevant to the photophysics of the "mobile" hydrogen atom on the S1 PE surface lead toward its dissociation from the molecule. There is no saddle-point for a "direct" proton transfer reaction on the S1 PE surface leading from the 2HP form to the 2PY form. The results confirm the hypothesis that the photo-induced dissociation-association (PIDA) mechanism is probably responsible for the excited-state tautomerization observed in this system.

UR - http://www.scopus.com/inward/record.url?scp=0030589433&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0030589433&partnerID=8YFLogxK

M3 - Article

VL - 213

SP - 193

EP - 201

JO - Chemical Physics

JF - Chemical Physics

SN - 0301-0104

IS - 1-3

ER -