This work describes the extension of a previously reported empirical localized orbital correction model from atomization energies, ionization potentials, electron affinities, and reaction enthalpies to the correction of barrier heights for chemical reactions involving molecules of first and second row elements. The B3LYP localized orbital correction version of the model (B3LYP-LOC) reduces the number of outliers and overall mean unsigned error (MUE) vs. experiment or ab initio values from 3.3 to 1.3 kcal/mole for barrier heights and from 5.5 to 1.2 kcal/mole for reaction enthalpies versus B3LYP. Furthermore, the new model has essentially zero additional computational cost beyond standard Density Functional Theory (DFT) calculations. Although the model is heuristic and is based on multiple linear regression to experimental or ab initio errors, each of the parameters is justified on physical grounds and provides insight into the fundamental limitations of DFT, most importantly the failure of current DFT methods to accurately account for nondynamical electron correlation.
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