TY - JOUR
T1 - Theoretical investigations of the proton transfer reaction in hydrogen-bonded complexes of cytosine with HNO
AU - Sobolewski, Andrzej L.
AU - Adamowicz, Ludwik
N1 - Funding Information:
This study was supportedb y a grant from the Office of Healtha nd EnvironmentaRle searcho f the Departmenotf Energy (No. DEFG 0393ER61605) and by a grant from the Committeefo r Scientific Researcho f Poland (No. 2 23959 203). LA would like to acknowledgae scholarshipfr om the Swedish NaturalS cienceR esearchC ounciland the hospitality of Professor,B jo6rn Roos and ProfessorA ndrzej Sadleja ndLund's theoreticaclh emistrgyr oupd uring his stay at the Departmenotf TheoreticaCl hemistry, Universityo f Lund.
PY - 1995/3/3
Y1 - 1995/3/3
N2 - 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.
AB - 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.
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U2 - 10.1016/0009-2614(95)00033-Z
DO - 10.1016/0009-2614(95)00033-Z
M3 - Article
AN - SCOPUS:0002289146
VL - 234
SP - 94
EP - 100
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-3
ER -