Gaussian-3 theory using reduced Mo/ller-Plesset order

TLDR

The authors introduce a variation of Gaussian‑3 theory that derives basis‑set extensions at the second‑order Møller–Plesset level. The resulting G3(MP2) method is evaluated on 299 energies from the G2/97 test set. G3(MP2) achieves average absolute deviations of 1.30 kcal mol⁻¹ (299 energies) and 1.18 kcal mol⁻¹ (148 neutral enthalpies), improving on G2(MP2)’s 1.89/2.03 and approaching full G3’s 1.01/0.94, while also reducing computational cost. References include J.

Abstract

A variation of Gaussian-3 (G3) theory is presented in which the basis set extensions are obtained at the second-order Mo/ller–Plesset level. This method, referred to as G3(MP2) theory, is assessed on 299 energies from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The average absolute deviation from experiment of G3(MP2) theory for the 299 energies is 1.30 kcal/mol and for the subset of 148 neutral enthalpies it is 1.18 kcal/mol. This is a significant improvement over the related G2(MP2) theory [J. Chem. Phys. 98, 1293 (1993)], which has an average absolute deviation of 1.89 kcal/mol for all 299 energies and 2.03 kcal/mol for the 148 neutral enthalpies. The corresponding average absolute deviations for full G3 theory are 1.01 and 0.94 kcal/mol, respectively. The new method provides significant savings in computational time compared to G3 theory and, also, G2(MP2) theory.