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Basis set error estimation for DFT calculations of electronic g‐tensors for transition metal complexes
Author(s) -
Pedersen Morten N.,
Hedegård Erik D.,
Kongsted Jacob
Publication year - 2014
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.23688
Subject(s) - basis set , basis (linear algebra) , computational chemistry , transition metal , set (abstract data type) , electronic structure , estimation , density functional theory , statistical physics , chemistry , mathematics , materials science , thermodynamics , computer science , physics , geometry , organic chemistry , engineering , systems engineering , catalysis , programming language
We present a detailed study of the basis set dependence of electronic g‐tensors for transition metal complexes calculated using Kohn–Sham density functional theory. Focus is on the use of locally dense basis set schemes where the metal is treated using either the same or a more flexible basis set than used for the ligand sphere. The performance of all basis set schemes is compared to the extrapolated complete basis set limit results. Furthermore, we test the performance of the aug‐cc‐pVTZ‐J basis set developed for calculations of NMR spin‐spin and electron paramagnetic resonance hyperfine coupling constants. Our results show that reasonable results can be obtain when using small basis sets for the ligand sphere, and very accurate results are obtained when an aug‐cc‐pVTZ basis set or similar is used for all atoms in the complex. © 2014 Wiley Periodicals, Inc.