The interaction between cytosine tautomers and water: An MP2 and coupled cluster electron correlation study

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Abstract

The complexation of cytosine with one water molecule was studied by quantum chemistry. The three lowest-energy tautomers, with three water binding positions for each, were considered and relative stabilities determined. MP2 geometries and CCSD(T) energies were calculated, using basis sets up to aug-cc-pVQZ. DFT calculations are also included. For all three tautomers, the favorite binding position of water is the O=C2-N1-H (H-O-C2=N1 in the enol form) moiety. Water binds to amino-keto 1.5-2.0 kcal/mol stronger than to the enol form and this roughly compensates for the energy difference in free monomers. Our methodological conclusion is that highest-level (coupled cluster) calculations should be used for the monomers, while MP2 or DFT calculations are satisfactory for describing the hydration itself. This way, our estimate for the relative energies of the complexes with respect to the amino-enol form is 0.0 to -0.5 kcal/mol for the amino-keto and 0.6-1.2 kcal/mol for imino-keto forms.

Original languageEnglish
Pages (from-to)383-390
Number of pages8
JournalChemical Physics Letters
Volume356
Issue number3-4
DOIs
Publication statusPublished - Apr 22 2002

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Electron correlations
Cytosine
tautomers
Water
Discrete Fourier transforms
water
electrons
monomers
Monomers
interactions
Quantum chemistry
energy
quantum chemistry
Complexation
Hydration
hydration
Molecules
Geometry
estimates
geometry

ASJC Scopus subject areas

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

Cite this

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abstract = "The complexation of cytosine with one water molecule was studied by quantum chemistry. The three lowest-energy tautomers, with three water binding positions for each, were considered and relative stabilities determined. MP2 geometries and CCSD(T) energies were calculated, using basis sets up to aug-cc-pVQZ. DFT calculations are also included. For all three tautomers, the favorite binding position of water is the O=C2-N1-H (H-O-C2=N1 in the enol form) moiety. Water binds to amino-keto 1.5-2.0 kcal/mol stronger than to the enol form and this roughly compensates for the energy difference in free monomers. Our methodological conclusion is that highest-level (coupled cluster) calculations should be used for the monomers, while MP2 or DFT calculations are satisfactory for describing the hydration itself. This way, our estimate for the relative energies of the complexes with respect to the amino-enol form is 0.0 to -0.5 kcal/mol for the amino-keto and 0.6-1.2 kcal/mol for imino-keto forms.",
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AU - Fogarasi, G.

AU - Szalay, P.

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N2 - The complexation of cytosine with one water molecule was studied by quantum chemistry. The three lowest-energy tautomers, with three water binding positions for each, were considered and relative stabilities determined. MP2 geometries and CCSD(T) energies were calculated, using basis sets up to aug-cc-pVQZ. DFT calculations are also included. For all three tautomers, the favorite binding position of water is the O=C2-N1-H (H-O-C2=N1 in the enol form) moiety. Water binds to amino-keto 1.5-2.0 kcal/mol stronger than to the enol form and this roughly compensates for the energy difference in free monomers. Our methodological conclusion is that highest-level (coupled cluster) calculations should be used for the monomers, while MP2 or DFT calculations are satisfactory for describing the hydration itself. This way, our estimate for the relative energies of the complexes with respect to the amino-enol form is 0.0 to -0.5 kcal/mol for the amino-keto and 0.6-1.2 kcal/mol for imino-keto forms.

AB - The complexation of cytosine with one water molecule was studied by quantum chemistry. The three lowest-energy tautomers, with three water binding positions for each, were considered and relative stabilities determined. MP2 geometries and CCSD(T) energies were calculated, using basis sets up to aug-cc-pVQZ. DFT calculations are also included. For all three tautomers, the favorite binding position of water is the O=C2-N1-H (H-O-C2=N1 in the enol form) moiety. Water binds to amino-keto 1.5-2.0 kcal/mol stronger than to the enol form and this roughly compensates for the energy difference in free monomers. Our methodological conclusion is that highest-level (coupled cluster) calculations should be used for the monomers, while MP2 or DFT calculations are satisfactory for describing the hydration itself. This way, our estimate for the relative energies of the complexes with respect to the amino-enol form is 0.0 to -0.5 kcal/mol for the amino-keto and 0.6-1.2 kcal/mol for imino-keto forms.

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