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We recently showed that dispersion-correcting potentials (DCPs),atom-centered Gaussian-type functions developed for use with B3LYP (J. Phys.Chem. Lett. 2012, 3, 1738-1744) greatly improved the ability of the underlyingfunctional to predict non-covalent interactions. However, the application ofB3LYP-DCP for the {\beta}-scission of the cumyloxyl radical led a calculatedbarrier height that was over-estimated by ca. 8 kcal/mol. We show in thepresent work that the source of this error arises from the previously developedcarbon atom DCPs, which erroneously alters the electron density in the C-Ccovalent-bonding region. In this work, we present a new C-DCP with a form thatwas expected to influence the electron density farther from the nucleus. Testsof the new C-DCP, with previously published H-, N- and O-DCPs, withB3LYP-DCP/6-31+G(2d,2p) on the S66, S22B, HSG-A, and HC12 databases ofnon-covalently interacting dimers showed that it is one of the most accuratemethods available for treating intermolecular interactions, giving meanabsolute errors (MAEs) of 0.19, 0.27, 0.16, and 0.18 kcal/mol, respectively.Additional testing on the S12L database of complexation systems gave an MAE of2.6 kcal/mol, showing that the B3LYP-DCP/6-31+G(2d,2p) approach is one of thebest-performing and feasible methods for treating large systems dominated bynon-covalent interactions. Finally, we showed that C-C making/breakingchemistry is well-predicted using the newly developed DCPs. In addition topredicting a barrier height for the {\beta}-scission of the cumyloxyl radicalthat is within 1.7 kcal/mol of the high-level value, application ofB3LYP-DCP/6-31+G(2d,2p) to 10 databases that include reaction barrier heightsand energies, isomerization energies and relative conformation energies givesperformance that is amongst the best of all available dispersion-correcteddensity-functional theory approaches.

Extension of the B3LYP - Dispersion-Correcting Potential Approach to the Accurate Treatment of both Inter- and Intramolecular Interactions