Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes

Handle URI:
http://hdl.handle.net/10754/576159
Title:
Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes
Authors:
Minenkov, Yury; Chermak, Edrisse ( 0000-0002-2716-5724 ) ; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
The performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Accuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes 2015:150827153751007 Journal of Chemical Theory and Computation
Publisher:
American Chemical Society (ACS)
Journal:
Journal of Chemical Theory and Computation
Issue Date:
27-Aug-2015
DOI:
10.1021/acs.jctc.5b00584
Type:
Article
ISSN:
1549-9618; 1549-9626
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.jctc.5b00584
Appears in Collections:
Articles; KAUST Catalysis Center (KCC); KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorChermak, Edrisseen
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-09-01T11:50:52Zen
dc.date.available2015-09-01T11:50:52Zen
dc.date.issued2015-08-27en
dc.identifier.citationAccuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexes 2015:150827153751007 Journal of Chemical Theory and Computationen
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.doi10.1021/acs.jctc.5b00584en
dc.identifier.urihttp://hdl.handle.net/10754/576159en
dc.description.abstractThe performance of the domain based local pair-natural orbital coupled-cluster (DLPNO-CCSD(T)) method has been tested to reproduce the experimental gas phase ligand dissociation enthalpy in a series of Cu+, Ag+ and Au+ complexes. For 33 Cu+ - non-covalent ligand dissociation enthalpies all-electron calculations with the same method result in MUE below 2.2 kcal/mol, although a MSE of 1.4 kcal/mol indicates systematic underestimation of the experimental values. Inclusion of scalar relativistic effects for Cu either via effective core potential (ECP) or Douglass-Kroll-Hess Hamiltonian, reduces the MUE below 1.7 kcal/mol and the MSE to -1.0 kcal/mol. For 24 Ag+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) method results in a mean unsigned error (MUE) below 2.1 kcal/mol and vanishing mean signed error (MSE). For 15 Au+ - non-covalent ligand dissociation enthalpies the DLPNO-CCSD(T) methods provides larger MUE and MSE, equal to 3.2 and 1.7 kcal/mol, which might be related to poor precision of the experimental measurements. Overall, for the combined dataset of 72 coinage metal ion complexes DLPNO-CCSD(T) results in a MUE below 2.2 kcal/mol and an almost vanishing MSE. As for a comparison with computationally cheaper density functional theory (DFT) methods, the routinely used M06 functional results in MUE and MSE equal to 3.6 and -1.7 kca/mol. Results converge already at CC-PVTZ quality basis set, making highly accurate DLPNO-CCSD(T) estimates to be affordable for routine calculations (single-point) on large transition metal complexes of > 100 atoms.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.jctc.5b00584en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/acs.jctc.5b00584.en
dc.subjectDLPNO-CCSD(T)en
dc.subjectTransition Metalsen
dc.subjectDissociation Enthalpiesen
dc.subjectBinding Energiesen
dc.subjectRelativistic Effectsen
dc.subjectM06en
dc.titleAccuracy of the DLPNO-CCSD(T) method for non-covalent bond dissociation enthalpies from coinage metal cation complexesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalJournal of Chemical Theory and Computationen
dc.eprint.versionPost-printen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorMinenkov, Yuryen
kaust.authorChermak, Edrisseen
kaust.authorCavallo, Luigien
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