Gaussian-2 theory using reduced Mo/ller–Plesset orders

TLDR

The paper presents two variations of Gaussian‑2 (G2) theory. The authors develop G2(MP2) and G2(MP3) methods, where basis‑set‑extension energy corrections are computed at MP2 and MP3 levels, respectively, and validate them on 125 benchmark systems. The G2(MP2) and G2(MP3) methods achieve average absolute deviations of 1.58 and 1.52 kcal/mol from experiment, slightly higher than the original G2 (1.21 kcal/mol), but offer substantial reductions in computational time and disk storage. The methods are validated on the 125‑system set used for G2 theory validation (J.

Abstract

Two variations of Gaussian-2 (G2) theory are presented. In the first, referred to as G2 (MP2) theory, the basis-set-extension energy corrections are obtained at the 2nd order Mo/ller–Plesset (MP2) level and in the second, referred to as G2(MP3) theory, they are obtained at the MP3 level. The methods are tested out on the set of 125 systems used for validation of G2 theory [J. Chem Phys. 94, 7221 (1991)]. The average absolute deviation of the G2(MP2) and G2(MP3) theories from experiment are 1.58 and 1.52 kcal/mol, respectively, compared to 1.21 kcal/mol for G2 theory. The new methods provide significant savings in computational time and disk storage.