Theoretical investigations of the proton transfer reaction in hydrogen-bonded complexes of cytosine with HNO

Andrzej L. Sobolewski, Ludwik Adamowicz

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The potential energy (PE) functions of the lowest singlet and triplet states of the hydrogen-bonded complexes of cytosine with HNO and NOH were theoretically investigated along the proton transfer (PT) coordinate. A full geometry optimization was performed along the PT reaction path at the Hartree-Fock level of theory. The energies at the optimized geometries were calculated with the use of second-order Møller-Plesset perturbation theory (MP2) and with second-order perturbation theory employing the complete active space self-consistent field wavefunction as the reference (CASPT2). It was found that the cyclic complex of the 'native' amino-oxo form of cytosine with NOH can be exothermally transformed on the barrierless PE surface into the complex of the 'rare' imino-oxo form with HNO. The results provide a model of a chemically induced PT reaction in nucleic acid bases which can effectively generate their 'rare' tautomeric forms.

Original languageEnglish (US)
Pages (from-to)94-100
Number of pages7
JournalChemical Physics Letters
Volume234
Issue number1-3
DOIs
StatePublished - Mar 3 1995
Externally publishedYes

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Proton transfer
Cytosine
Hydrogen
protons
hydrogen
perturbation theory
potential energy
Potential energy functions
Potential energy surfaces
Geometry
nucleic acids
Wave functions
geometry
Nucleic Acids
atomic energy levels
self consistent fields
optimization
energy

ASJC Scopus subject areas

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

Cite this

Theoretical investigations of the proton transfer reaction in hydrogen-bonded complexes of cytosine with HNO. / Sobolewski, Andrzej L.; Adamowicz, Ludwik.

In: Chemical Physics Letters, Vol. 234, No. 1-3, 03.03.1995, p. 94-100.

Research output: Contribution to journalArticle

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