Title

The correlation consistent composite approach (ccCA): An alternative to the Gaussian-n methods

Abstract

An alternative to the Gaussian-n (G1, G2, and G3) composite methods of computing molecular energies is proposed and is named the "correlation consistent composite approach" (ccCA, ccCA-CBS-1, ccCA-CBS-2). This approach uses the correlation consistent polarized valence (cc-pV XZ) basis sets. The G2-1 test set of 48 enthalpies of formation (ΔH f), 38 adiabatic ionization potentials (IPs), 25 adiabatic electron affinities (EAs), and 8 adiabatic proton affinities (PAs) are computed using this approach, as well as the ΔH f values of 30 more systems. Equilibrium molecular geometries and vibrational frequencies are obtained using B3LYP density functional theory. When applying the ccCA-CBS method with the cc-pVXZ series of basis sets augmented with diffuse functions, mean absolute deviations within the G2-1 test set compared to experiment are 1.33 kcal mol -1 for ΔH f, 0.81 kcal mol -1 for IPs, 1.02 kcal mol -1 for EAs, and 1.51 kcal mol -1 for PAs, without including the "high-level correction" (HLC) contained in the original Gn methods. Whereas the HLC originated in the Gaussian-1 method as an isogyric correction, it evolved into a fitted parameter that minimized the error of the composite methods, eliminating its physical meaning. Recomputing the G1 and G3 enthalpies of formation without the HLC reveals a systematic trend where most ΔH f values are significantly higher than experimental values. By extrapolating electronic energies to the complete basis set (CBS) limit and adding G3-like corrections for the core-valence and infinite-order electron correlation effects, ccCA-CBS-2 often underestimates the experimental ΔH f, especially for larger systems. This is desired as inclusion of relativistic and atomic spin-orbit effects subsequently improves theoretical ΔH f values to give a 0.81 kcal mol -1 mean absolute deviation with ccCA-CBS-2. The ccCA-CBS method is a viable "black box" method that can be used on systems with at least 10-15 heavy atoms. © 2006 American Institute of Physics.

Publication Title

Journal of Chemical Physics

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