Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
Org Lett. 2017 May 19;19(10):2576-2579. doi: 10.1021/acs.orglett.7b00891. Epub 2017 May 5.
The failure of available density functional methods to compute accurate reaction enthalpies of common organic reactions is well documented. Herein, we demonstrate that the disparate results from different functionals stem from the systematic errors in the underlying elementary reactions that represent the changes in the bonding environment between reactants and products. We develop a rigorous protocol to correct for these systematic errors and obtain dramatically improved results with deviations of only 1-2 kcal/mol for most functionals.
已有密度泛函方法在计算常见有机反应的准确反应焓方面的失败已有充分记录。在此，我们证明不同功能的不同结果源于代表反应物和产物之间键合环境变化的基本反应中的系统误差。我们开发了一种严格的协议来纠正这些系统误差，并获得了显著改善的结果，大多数功能的偏差仅为 1-2 kcal/mol。
