{ "dc.contributor.author": "Güell Serra, Mireia" , "dc.contributor.author": "Luis Luis, Josep Maria" , "dc.contributor.author": "Solà i Puig, Miquel" , "dc.contributor.author": "Swart, Marcel" , "dc.date.accessioned": "2019-05-06T08:12:28Z" , "dc.date.available": "2019-05-06T08:12:29Z" , "dc.date.issued": "2008-06-24" , "dc.identifier.issn": "1089-5639" , "dc.identifier.uri": "http://hdl.handle.net/10256/16574" , "dc.description.abstract": "We have performed a systematic investigation of the influence of the basis set on relative spin-state energies for a number of iron compounds. In principle, with an infinitely large basis set, both Slater-type orbital (STO) and Gaussian-type orbital (GTO) series should converge to the same final answer, which is indeed what we observe for both vertical and relaxed spin-state splittings. However, we see throughout the paper that the STO basis sets give consistent and rapidly converging results, while the convergence with respect to the basis set size is much slower for the GTO basis sets. For example, the large GTO basis sets that give good results for the vertical spin-state splittings of compounds 1-3 (6- 311+G**, Ahlrichs VTZ2D2P), fail for the relaxed spin-state splittings of compound 4. Very demanding GTO basis sets like Dunning's correlation consistent (cc-pVTZ, cc-pVQZ) basis sets are needed to achieve good results for these relaxed spin-states. The use of popular (Pople-type) GTO, Effective Core Potentials Basis-set (ECPB) or mixed ECPB(Fe):GTO(rest) basis sets is shown to lead to substantial deviations (2-10 kcal/mol, 14-24 kcal/mol for 3-21G), in particular for the high spin-states that are typically placed at too low energy. Moreover, the use of an effective core potential in the ECPB basis sets results in spin-state splittings that are systematically different from the STO-GTO results" , "dc.description.sponsorship": "This study was financially supported by the Spanish research project CTQ2005-08797-C02-01/BQU and the DURSI project nr. 2005SGR-00238. MG thanks MEC for a research grant" , "dc.format.extent": "8 p." , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "American Chemical Society (ACS)" , "dc.relation": "MEC/PN 2005-2008/CTQ2005-08797-C02-01" , "dc.relation.isformatof": "Versió postprint del document publicat a: https://doi.org/10.1021/jp803441m" , "dc.relation.ispartof": "© Journal of Physical Chemistry A, 2008, vol. 112, núm. 8, p. 6384-6391" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.source": "Güell Serra, Mireia Luis Luis, Josep Maria Solà i Puig, Miquel Swart, Marcel 2008 Importance of the basis set for the spin-state energetics of iron complexes Journal of Physical Chemistry A 112 8 6384 6391" , "dc.subject": "Funcional de densitat, Teoria del" , "dc.subject": "Density functionals" , "dc.subject": "Polarització (Física nuclear)" , "dc.subject": "Polarization (Nuclear physics)" , "dc.subject": "Orbitals moleculars" , "dc.subject": "Molecular orbitals" , "dc.title": "Importance of the basis set for the spin-state energetics of iron complexes" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.type.version": "info:eu-repo/semantics/acceptedVersion" , "dc.identifier.doi": "https://doi.org/10.1021/jp803441m" , "dc.identifier.idgrec": "009760" , "dc.contributor.funder": "Ministerio de Educación y Ciencia (Espanya)" , "dc.type.peerreviewed": "peer-reviewed" , "dc.identifier.eissn": "1520-5215" }