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Optimal diffuse augmented atomic basis sets for extrapolation of the correlation energy
Author(s) -
Varandas António J. C.,
Pansini Fernando N. N.
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26135
Subject(s) - extrapolation , basis (linear algebra) , basis set , bond dissociation energy , ionization energy , chemistry , limit (mathematics) , statistical physics , computational chemistry , ionization , atomic physics , quantum mechanics , dissociation (chemistry) , mathematics , physics , mathematical analysis , density functional theory , geometry , ion
We seek correlation‐consistent diffuse‐augmented double‐zeta and triple‐zeta basis sets that perform optimally in extrapolating the correlation energy to the one‐electron complete basis set limit, denoted oAV X Z and oAV( X + d )Z. The novel basis sets are method‐dependent in that they are trained to perform optimally for the correlation energy at each specific level of theory. They are shown to yield accurate results in calculating both the energy and tensorial properties such as polarizabilities while not significantly altering the Hartree‐Fock energy. Quantitatively, complete basis set limit (CBS)‐/(oAV d Z,oAV t Z)‐extrapolated correlation energies typically outperform, by 3‐ to 5‐fold, the ones calculated with traditional ansatzes of similar flexibility. Attaining energies of CBS/(AV t Z,AV q Z) type or better accuracy, they frequently outperform expensive raw explicitly correlated ones. Promisingly, a limited test on CBS‐extrapolated energies based on conventional basis sets has shown that they compare well even with extrapolated explicitly correlated ones. Calculated atomization and dissociation energies, molecular geometries, ionization potentials, and electron affinities also tend to outperform the ones obtained with traditional Dunning's ansatzes from which the new basis sets have been determined. The method for basis set generation is simple, and there is no reason of principle why the approach could not be adapted for handling other bases in the literature.