Influence of the complete basis set approximation, tight weighted-core, and diffuse functions on the DLPNO-CCSD(T1) atomization energies of neutral H,C,O-compounds

by Yury Minenkov, Luigi Cavallo, Kirk A. Peterson
Year: 2023 DOI: https://doi.org/10.1002/jcc.27033

Extra Information

J.Comput.Chem.

Abstract

The impact of complete basis set extrapolation schemes (CBS), diffuse functions, and tight weighted-core functions on enthalpies of formation predicted via the DLPNO-CCSD(T1) reduced Feller-Peterson-Dixon approach has been examined for neutral H,C,O-compounds. All tested three-point (TZ/QZ/5Z) extrapolation schemes result in mean unsigned deviation (MUD) below 2 kJ mol−1 relative to the experiment. The two-point QZ/5Z and TZ/QZ CBS  extrapolation schemes are inferior to their inverse power counterpart () by 1.3 and 4.3 kJ mol−1. The CBS extrapolated frozen core atomization energies are insensitive (within 1 kJ mol−1) to augmentation of the basis set with tight weighted core functions. The core-valence correlation effects converge already at triple-ζ, although double-ζ/triple-ζ CBS extrapolation performs better and is recommended. The effect of diffuse function augmentation converges slowly, and cannot be reproduced with double- ζ or triple- ζ calculations as these are plagued with basis set superposition and incompleteness errors.

Keywords

atomization energies basis set diffuse functions DLPNO-CCSD(T1 enthalpy of formation