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Revisiting the extrapolation of correlation energies to complete basis set limit
Author(s) -
Okoshi Masaki,
Atsumi Teruo,
Nakai Hiromi
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23896
Subject(s) - extrapolation , mathematics , limit (mathematics) , scaling , gaussian , basis (linear algebra) , cardinal number (linguistics) , function (biology) , basis function , set (abstract data type) , basis set , statistical physics , mathematical analysis , physics , quantum mechanics , geometry , computer science , linguistics , philosophy , evolutionary biology , biology , programming language , molecule
The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double‐zeta (DZ) and triple‐zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian‐3X and Gaussian‐2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts. © 2015 Wiley Periodicals, Inc.