The correlation consistent composite approach (cc CA): 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-pVXZ) basis sets. The G2-1 test set of 48 enthalpies of formation (ΔHf), 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 ΔHf 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 1.33kcalmol−1 for ΔHf,0.81kcalmol−1 for IPs, 1.02kcalmol−1 for EAs, and 1.51kcalmol−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 ΔHf 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 ΔHf, especially for larger systems. This is desired as inclusion of relativistic and atomic spin-orbit effects subsequently improves theoretical ΔHf values to give a 0.81kcalmol−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.