Abstract
Density-functional theory (DFT) is currently the most popular method for modeling non-covalent
interactions and thermochemistry. The accurate calculation of non-covalent interaction energies, reaction
energies, and barrier heights requires choosing an appropriate functional and, typically, a relatively large
basis set. Deficiencies of the density-functional approximation and the use of a limited basis set are the
leading sources of error in the calculation of non-covalent and thermochemical properties in molecular
systems. In this article, we present three new DFT methods based on the BLYP, M062X and CAM-B3LYP
functionals in combination with the 6-31G* basis set and corrected with atom-centered potentials (ACPs).
ACPs are one-electron potentials that have the same form as effective-core potentials, except they do not
replace any electrons. The ACPs developed in this work are used to generate energy corrections to the
underlying DFT/basis-set method such that the errors in predicted chemical properties are minimized while
maintaining the low computational cost of the parent methods. ACPs were developed for the elements H,
B, C, N, O, F, Si, P, S, and Cl. The ACP parameters were determined using an extensive training set of
118,655 data points, mostly of complete basis set coupled-cluster level quality. The target molecular
properties for the ACP-corrected methods include non-covalent interaction energies, molecular
conformational energies, reaction energies, barrier heights, and bond separation energies. The ACPs were
tested first on the training set and then on a validation set of 42,567 additional data points. We show that
the ACP-corrected methods can predict the target molecular properties with accuracy close to complete
basis set wavefunction theory methods, but at a computational cost of double-ζ DFT methods. This makes
the new BLYP/6-31G*-ACP, M062X/6-31G*-ACP, and CAM-B3LYP/6-31G*-ACP methods uniquely
suited to the calculation of non-covalent, thermochemical, and kinetic properties in large molecular
systems.
Supplementary materials
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