DENSITY-FUNCTIONAL STUDY OF INTRINSIC AND ENVIRONMENTAL-EFFECTS IN THE TAUTOMERIC EQUILIBRIUM OF 2-PYRIDONE

被引：102

作者：

BARONE, V ^{[1
]}

ADAMO, C ^{[1
]}

机构：

[1] UNIV BASILICATA, DIPARTIMENTO CHIM, I-85100 POTENZA, ITALY

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1995年 / 99卷 / 41期

关键词：

D O I：

10.1021/j100041a022

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 mechanism of oxo/hydroxy tautomerization in 2-pyridone has been investigated by means of a self-consistent density functional/Hartree-Fock (HF) hybrid method with particular attention to the role of solvent effects. The computed structural parameters, reaction heats, and energy barriers are in good agreement with the values obtained from post-HF models. Specific interactions with a single water molecule strongly enhance the reaction rate and shift the equilibrium toward the lactam form, while the effect of bulk solvent is comparatively negligible. Zero point and entropy effects do not modify the above general trends. The interaction between both tautomeric forms and a water molecule has been analyzed by means of the so called natural bond orbital approach.

引用

页码：15062 / 15068

页数：7

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