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Auxiliary basis sets for density‐fitting second‐order Møller–Plesset perturbation theory: Weighted core‐valence correlation consistent basis sets for the 4 d elements Y–Pd
Author(s) -
Hill J. Grant
Publication year - 2013
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.23372
Subject(s) - basis set , møller–plesset perturbation theory , coupled cluster , perturbation theory (quantum mechanics) , valence (chemistry) , basis (linear algebra) , electronic correlation , chemistry , perturbation (astronomy) , basis function , mathematics , statistical physics , physics , quantum mechanics , density functional theory , computational chemistry , electron , molecule , geometry
Auxiliary basis sets (ABS) specifically matched to the cc‐pwCV n Z‐PP and aug‐cc‐pwCV n Z‐PP orbital basis sets (OBS) have been developed and optimized for the 4 d elements Y‐Pd at the second‐order Møller‐Plesset perturbation theory level. Calculation of the core‐valence electron correlation energies for small to medium sized transition metal complexes demonstrates that the error due to the use of these new sets in density fitting is three to four orders of magnitude smaller than that due to the OBS incompleteness, and hence is considered negligible. Utilizing the ABSs in the resolution‐of‐the‐identity component of explicitly correlated calculations is also investigated, where it is shown that i ‐type functions are important to produce well‐controlled errors in both integrals and correlation energy. Benchmarking at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations level indicates impressive convergence with respect to basis set size for the spectroscopic constants of 4 d monofluorides; explicitly correlated double‐ζ calculations produce results close to conventional quadruple‐ζ, and triple‐ζ is within chemical accuracy of the complete basis set limit. © 2013 Wiley Periodicals, Inc.