Bond-based corrections to semi-empirical and ab initio electronic structure calculations

A simple, empirical, bond-based correction method improves the accuracy of several types of electronic structure calculations in predicting heats of formation. The optimal corrections for common types of bonds are determined by minimizing the deviations from experimental thermochemical data. The method is tested with the 223-species of the G3/99 test set of Curtiss et al. For the subset of 155 species containing only bonds in the set of 15 bonds for which corrections are made, the mean absolute error is reduced from 142 to 1.84 for LSDA, from 0.81 to 0.61 for G3, from 4.65 to 1.48 for B3LYP, from 5.54 to 1.94 for TPSS, and from 3.51 to 1.76 for TPSSh (all in kcal/mol). (C) 2004 Elsevier B.V. All rights reserved.