On the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: The role of dispersive interactions

Handle URI:
http://hdl.handle.net/10754/561963
Title:
On the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: The role of dispersive interactions
Authors:
Jacobsen, Heiko; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
The performance of a series of density functionals when tested on the prediction of the phosphane substitution energy of transition metal complexes is evaluated. The complexes Fe-BDA and Ru-COD (BDA=benzylideneacetone, COD=cyclooctadiene) serve as reference systems, and calculated values are compared with the experimental values in THF as obtained from calorimetry. Results clearly indicate that functionals specifically developed to include dispersion interactions usually outperform other functionals when BDA or COD substitution is considered. However, when phosphanes of different sizes are compared, functionals including dispersion interactions, at odd with experimental evidence, predict that larger phosphanes bind more strongly than smaller phosphanes, while functionals not including dispersion interaction reproduce the experimental trends with reasonable accuracy. In case of the DFT-D functionals, inclusion of a cut-off distance on the dispersive term resolves this issue, and results in a rather robust behavior whatever ligand substitution reaction is considered. Ne quid nimis: Describing chemical reactions in solution by computational techniques developed for gas-phase scenarios might produce erroneous results (see histogram). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Wiley-Blackwell
Journal:
ChemPhysChem
Issue Date:
23-Dec-2011
DOI:
10.1002/cphc.201100705
Type:
Article
ISSN:
14394235
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorJacobsen, Heikoen
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T09:35:08Zen
dc.date.available2015-08-03T09:35:08Zen
dc.date.issued2011-12-23en
dc.identifier.issn14394235en
dc.identifier.doi10.1002/cphc.201100705en
dc.identifier.urihttp://hdl.handle.net/10754/561963en
dc.description.abstractThe performance of a series of density functionals when tested on the prediction of the phosphane substitution energy of transition metal complexes is evaluated. The complexes Fe-BDA and Ru-COD (BDA=benzylideneacetone, COD=cyclooctadiene) serve as reference systems, and calculated values are compared with the experimental values in THF as obtained from calorimetry. Results clearly indicate that functionals specifically developed to include dispersion interactions usually outperform other functionals when BDA or COD substitution is considered. However, when phosphanes of different sizes are compared, functionals including dispersion interactions, at odd with experimental evidence, predict that larger phosphanes bind more strongly than smaller phosphanes, while functionals not including dispersion interaction reproduce the experimental trends with reasonable accuracy. In case of the DFT-D functionals, inclusion of a cut-off distance on the dispersive term resolves this issue, and results in a rather robust behavior whatever ligand substitution reaction is considered. Ne quid nimis: Describing chemical reactions in solution by computational techniques developed for gas-phase scenarios might produce erroneous results (see histogram). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.publisherWiley-Blackwellen
dc.subjectdensity functional calculationsen
dc.subjectdispersion energyen
dc.subjectphosphane ligandsen
dc.subjectthermochemistryen
dc.subjecttransition metalsen
dc.titleOn the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: The role of dispersive interactionsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalChemPhysChemen
dc.contributor.institutionKemKom, 1215 Ursulines Avenue, New Orleans, LA 70116, United Statesen
kaust.authorCavallo, Luigien
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