Ab initio calculations of absolute pKa values in aqueous solution I.: Carboxylic acids

被引:144
作者
da Silva, CO [1 ]
da Silva, EC [1 ]
Nascimento, MAC [1 ]
机构
[1] Univ Fed Rio de Janeiro, Inst Quim, Dept Quim Fis, BR-21949900 Rio De Janeiro, Brazil
关键词
D O I
10.1021/jp9836473
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
A thermodynamical cycle is proposed to calculate absolute pK(a) values for a Bronsted acid in aqueous solution. The solvent (water) was represented by a dielectric using the polarizable continuum model (PCM), and the absolute pK(a) values of some aliphatic carboxylic acids were computed. The results indicate that the proposed methodology seems to be capable of predicting reasonably good absolute pK(a) values, although in some cases appreciable deviations are observed, which can be related to neglecting the molecular motion contributions (Delta G(Mm)) to the solvation energy (Delta G(solv)).
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页码:11194 / 11199
页数:6
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