Theoretical calculations and matrix-isolation FT-IR studies of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 7. 2-Hydroxypyridine/2-oxopyridine complexes with H2O

Ahmed Dkhissi, Linda Houben, Johan Smets, Ludwik Adamowicz, Guido Macs

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Abstract

The H-bond interaction between the tautomeric cytosine-modeling system, 2-hydroxypyridine (2HP)/2-oxopyridine (2OP), with water is investigated using matrix-isolation FT-IR spectroscopy and ab initio calculations performed with the RHF and MP2 methods and the DFT method with the B3-LYP hybrid functional. Equilibrium structures of six different complexes have been found in the calculations. The theoretical results indicate that the closed N⋯H-O⋯H-O and C=O⋯H-O⋯H-N H-bonded water complexes are the most stable systems for the 2HP and the 2OP tautomers, respectively. Both closed complexes as well as the three open complexes O-H⋯OH2, N⋯H-OH, and C=O⋯H-OH have been identified in the experimental spectrum. A detailed analysis of the structural, energetic and vibrational parameters for the closed complexes has been performed. Both in the matrix (Ar) and in the gas phase, the hydroxy tautomer, 2HP, is more stable than the oxo form, 2OP. An important observation is that addition of a single water molecule shifts the tautomeric equilibrium toward the oxo 2OP form, which is in agreement with the theoretical calculations.

Original languageEnglish (US)
Pages (from-to)9785-9792
Number of pages8
JournalJournal of Physical Chemistry A
Volume104
Issue number43
StatePublished - Nov 2 2000

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Cytosine
tautomers
Hydrogen
isolation
Molecules
hydrogen
matrices
water
Water
molecules
Discrete Fourier transforms
vapor phases
Infrared spectroscopy
Gases
shift
spectroscopy
2-hydroxypyridine
hydroxide ion
isocytosine
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Theoretical calculations and matrix-isolation FT-IR studies of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 7. 2-Hydroxypyridine/2-oxopyridine complexes with H2O",
abstract = "The H-bond interaction between the tautomeric cytosine-modeling system, 2-hydroxypyridine (2HP)/2-oxopyridine (2OP), with water is investigated using matrix-isolation FT-IR spectroscopy and ab initio calculations performed with the RHF and MP2 methods and the DFT method with the B3-LYP hybrid functional. Equilibrium structures of six different complexes have been found in the calculations. The theoretical results indicate that the closed N⋯H-O⋯H-O and C=O⋯H-O⋯H-N H-bonded water complexes are the most stable systems for the 2HP and the 2OP tautomers, respectively. Both closed complexes as well as the three open complexes O-H⋯OH2, N⋯H-OH, and C=O⋯H-OH have been identified in the experimental spectrum. A detailed analysis of the structural, energetic and vibrational parameters for the closed complexes has been performed. Both in the matrix (Ar) and in the gas phase, the hydroxy tautomer, 2HP, is more stable than the oxo form, 2OP. An important observation is that addition of a single water molecule shifts the tautomeric equilibrium toward the oxo 2OP form, which is in agreement with the theoretical calculations.",
author = "Ahmed Dkhissi and Linda Houben and Johan Smets and Ludwik Adamowicz and Guido Macs",
year = "2000",
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T1 - Theoretical calculations and matrix-isolation FT-IR studies of hydrogen-bonded complexes of molecules modeling cytosine or isocytosine tautomers. 7. 2-Hydroxypyridine/2-oxopyridine complexes with H2O

AU - Dkhissi, Ahmed

AU - Houben, Linda

AU - Smets, Johan

AU - Adamowicz, Ludwik

AU - Macs, Guido

PY - 2000/11/2

Y1 - 2000/11/2

N2 - The H-bond interaction between the tautomeric cytosine-modeling system, 2-hydroxypyridine (2HP)/2-oxopyridine (2OP), with water is investigated using matrix-isolation FT-IR spectroscopy and ab initio calculations performed with the RHF and MP2 methods and the DFT method with the B3-LYP hybrid functional. Equilibrium structures of six different complexes have been found in the calculations. The theoretical results indicate that the closed N⋯H-O⋯H-O and C=O⋯H-O⋯H-N H-bonded water complexes are the most stable systems for the 2HP and the 2OP tautomers, respectively. Both closed complexes as well as the three open complexes O-H⋯OH2, N⋯H-OH, and C=O⋯H-OH have been identified in the experimental spectrum. A detailed analysis of the structural, energetic and vibrational parameters for the closed complexes has been performed. Both in the matrix (Ar) and in the gas phase, the hydroxy tautomer, 2HP, is more stable than the oxo form, 2OP. An important observation is that addition of a single water molecule shifts the tautomeric equilibrium toward the oxo 2OP form, which is in agreement with the theoretical calculations.

AB - The H-bond interaction between the tautomeric cytosine-modeling system, 2-hydroxypyridine (2HP)/2-oxopyridine (2OP), with water is investigated using matrix-isolation FT-IR spectroscopy and ab initio calculations performed with the RHF and MP2 methods and the DFT method with the B3-LYP hybrid functional. Equilibrium structures of six different complexes have been found in the calculations. The theoretical results indicate that the closed N⋯H-O⋯H-O and C=O⋯H-O⋯H-N H-bonded water complexes are the most stable systems for the 2HP and the 2OP tautomers, respectively. Both closed complexes as well as the three open complexes O-H⋯OH2, N⋯H-OH, and C=O⋯H-OH have been identified in the experimental spectrum. A detailed analysis of the structural, energetic and vibrational parameters for the closed complexes has been performed. Both in the matrix (Ar) and in the gas phase, the hydroxy tautomer, 2HP, is more stable than the oxo form, 2OP. An important observation is that addition of a single water molecule shifts the tautomeric equilibrium toward the oxo 2OP form, which is in agreement with the theoretical calculations.

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