Accurate prediction of enthalpies of formation for a large set of organic compounds

This article describes a multiparameter calibration model, which improves the accuracy of density functional theory (DFT) for the prediction of standard enthalpies of formation for a large set of organic compounds. The model applies atom based, bond based, electronic, and radical environmental correction terms to calibrate the calculated enthalpies of formation at B3LYP/6-31G(d,p) level by a least-square method. A diverse data set of 771 closed-shell compounds and radicals is used to train the model. The leave-one-out cross validation squared correlation coefficient q(2) of 0.84 and squared correlation coefficient r(2) of 0.86 for the final model are obtained. The mean absolute error in enthalpies of formation for the dataset is reduced from 4.9 kcal/mol before calibration to 2.1 kcal/mol after calibration. Five-fold cross validation is also used to estimate the performance of the calibration model and similar results are obtained.