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 (Formula presented.) extrapolation schemes are inferior to their inverse power counterpart ((Formula presented.)) 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.
Bibliographical noteKAUST Repository Item: Exported on 2022-12-01
Acknowledgements: We gratefully acknowledge the anonymous reviewers of this work for their useful comments and suggestions. The work was financially supported by the Russian Science Foundation (project 22-23-20206). Luigi Cavallo gratefully acknowledges the financial support from King Abdullah University of Science and Technology (KAUST). Kirk A. Peterson gratefully acknowledges support from the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program grant no. DE-SC0008501. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia and the Joint Supercomputer Center of RAS in Moscow, Russia.
ASJC Scopus subject areas
- Computational Mathematics
- General Chemistry