Ab initio study of intramolecular proton transfer reactions in cytosine

被引:25
作者
Morpurgo, S [1 ]
Bossa, M [1 ]
Morpurgo, GO [1 ]
机构
[1] Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy
关键词
D O I
10.1016/S0009-2614(97)01157-3
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The activation energies of intramolecular proton transfer reactions of cytosine in the gas phase were computed through ab initio calculations. MP2/6-31G** and MP2/D95** energy calculations were performed over geometries obtained at the HF/3-21G, HF/6-31G(N8*) and HF/D95(N8*) level (d-type polarisation functions were added on the N8 atom). Corrections for the zero-point vibrational energy were included. It is suggested that not only thermodynamic but also kinetic factors may be responsible for the distribution of the tautomeric species in the gas phase. Results are discussed with reference to spectroscopic data in the literature. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:233 / 238
页数:6
相关论文
共 23 条
[1]  
ATKINS PW, 1982, PHYSICAL CHEM
[2]   CRYSTAL STRUCTURE OF CYTOSINE [J].
BARKER, DL ;
MARSH, RE .
ACTA CRYSTALLOGRAPHICA, 1964, 17 (12) :1581-&
[3]   TAUTOMERS OF CYTOSINE BY MICROWAVE SPECTROSCOPY [J].
BROWN, RD ;
GODFREY, PD ;
MCNAUGHTON, D ;
PIERLOT, AP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (06) :2308-2310
[4]   A THEORETICAL-STUDY OF TAUTOMERISM IN THE GAS-PHASE AND AQUEOUS-SOLUTION - A COMBINED USE OF STATE-OF-THE-ART ABINITIO QUANTUM-MECHANICS AND FREE-ENERGY PERTURBATION-METHODS [J].
CIEPLAK, P ;
BASH, P ;
SINGH, UC ;
KOLLMAN, PA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6283-6289
[5]   Tautomerism and protonation of guanine and cytosine. Implications in the formation of hydrogen-bonded complexes [J].
Colominas, C ;
Luque, FJ ;
Orozco, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (29) :6811-6821
[6]   TAUTOMERISM IN CYTOSINE AND 3-METHYLCYTOSINE - THERMODYNAMIC AND KINETIC STUDY [J].
DREYFUS, M ;
BENSAUDE, O ;
DODIN, G ;
DUBOIS, JE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (20) :6338-6349
[7]  
Frisch M.J., 1995, GAUSSIAN 94 REVISION
[8]  
Frisch M.J., 1995, GAUSSIAN 94 USERS RE
[9]   A THEORETICAL-STUDY USING ABINITIO METHODS OF TAUTOMERISM IN CYTOSINE IN THE GAS-PHASE AND IN WATER [J].
GOULD, IR ;
GREEN, DVS ;
YOUNG, P ;
HILLIER, IH .
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (16) :4434-4437
[10]   TAUTOMERISM IN URACIL, CYTOSINE AND GUANINE - A COMPARISON OF ELECTRON CORRELATION PREDICTED BY AB-INITIO AND DENSITY-FUNCTIONAL THEORY METHODS [J].
GOULD, IR ;
BURTON, NA ;
HALL, RJ ;
HILLIER, IH .
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1995, 331 (1-2) :147-154