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Article: Relativistic-consistent electron densities of the coinage metal clusters M 2, M 4, M 4 2-, and M 4Na 2 (M = Cu, Ag, Au): A QTAIM study

TitleRelativistic-consistent electron densities of the coinage metal clusters M 2, M 4, M 4 2-, and M 4Na 2 (M = Cu, Ag, Au): A QTAIM study
Authors
Issue Date2011
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpca
Citation
Journal Of Physical Chemistry A, 2011, v. 115 n. 45, p. 13024-13035 How to Cite?
AbstractWe employ second-order Møller-Plesset perturbation theory level in combination with recently developed pseudopotential-based correlation consistent basis sets to obtain accurate relativistic-consistent electron densities for small coinage metal clusters. Using calculated electron densities, we employ Bader's quantum theory of atoms in molecules (QTAIM) to gain insights into the nature of metal-metal bonding in the clusters M 2, M 4, M 4 2-, and M 4Na 2 (M = Cu, Ag, Au). For the simplest case of the metal dimer, M 2, we correlate the strength of the metal-metal bond with the value of the electron density at the bond critical point, the total energy density at the bond critical point, the sharing (delocalization) index, and the values of the two principle negative curvatures. We then consider changes to the metal-metal bonding and charge density distribution upon the addition of two metal atoms to form the metal tetramer, M 4, and then followed by the addition of an electron pair to form M 4 2- and finally followed by the addition of two alkali metal (sodium) ions to form M 4Na 2. Using topological properties of the electron density, we present evidence for the existence of σ-aromaticity in Au 4 2-. We also report the existence of two non-nuclear attractors in the molecular graph of Cu 4 2- and large negative charge accumulation in the nonbonded Cu basins of this cluster. © 2011 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/151341
ISSN
2015 Impact Factor: 2.883
2015 SCImago Journal Rankings: 1.231
ISI Accession Number ID
Funding AgencyGrant Number
Hong Kong UGCSEG HKU09
GRF HKU 702608P
Natural Sciences and Engineering Research Council of Canada (NSERC)
Canada Foundation for Innovation (CFI)
Mount Saint Vincent University
Funding Information:

The authors thank Dr. Todd A. Keith for drawing their attention to the existence of the non-nuclear attractor in the Cu<INF>4</INF>2- cluster and for very helpful discussions. The authors also thank Professor Kirk Peterson and Professor Markus Reiher for valuable comments and suggestions. This research has been supported by funding from a Hong Kong UGC Special Equipment Grant (SEG HKU09) and GRF HKU 702608P, the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canada Foundation for Innovation (CFI), and an internal research grant from Mount Saint Vincent University.

References

 

DC FieldValueLanguage
dc.contributor.authorSadjadi, Sen_US
dc.contributor.authorMatta, CFen_US
dc.contributor.authorLemke, KHen_US
dc.contributor.authorHamilton, IPen_US
dc.date.accessioned2012-06-26T06:20:51Z-
dc.date.available2012-06-26T06:20:51Z-
dc.date.issued2011en_US
dc.identifier.citationJournal Of Physical Chemistry A, 2011, v. 115 n. 45, p. 13024-13035en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/10722/151341-
dc.description.abstractWe employ second-order Møller-Plesset perturbation theory level in combination with recently developed pseudopotential-based correlation consistent basis sets to obtain accurate relativistic-consistent electron densities for small coinage metal clusters. Using calculated electron densities, we employ Bader's quantum theory of atoms in molecules (QTAIM) to gain insights into the nature of metal-metal bonding in the clusters M 2, M 4, M 4 2-, and M 4Na 2 (M = Cu, Ag, Au). For the simplest case of the metal dimer, M 2, we correlate the strength of the metal-metal bond with the value of the electron density at the bond critical point, the total energy density at the bond critical point, the sharing (delocalization) index, and the values of the two principle negative curvatures. We then consider changes to the metal-metal bonding and charge density distribution upon the addition of two metal atoms to form the metal tetramer, M 4, and then followed by the addition of an electron pair to form M 4 2- and finally followed by the addition of two alkali metal (sodium) ions to form M 4Na 2. Using topological properties of the electron density, we present evidence for the existence of σ-aromaticity in Au 4 2-. We also report the existence of two non-nuclear attractors in the molecular graph of Cu 4 2- and large negative charge accumulation in the nonbonded Cu basins of this cluster. © 2011 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jpcaen_US
dc.relation.ispartofJournal of Physical Chemistry Aen_US
dc.titleRelativistic-consistent electron densities of the coinage metal clusters M 2, M 4, M 4 2-, and M 4Na 2 (M = Cu, Ag, Au): A QTAIM studyen_US
dc.typeArticleen_US
dc.identifier.emailLemke, KH:kono@hkucc.hku.hken_US
dc.identifier.authorityLemke, KH=rp00729en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jp204993ren_US
dc.identifier.scopuseid_2-s2.0-80855156891en_US
dc.identifier.hkuros195661-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-80855156891&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume115en_US
dc.identifier.issue45en_US
dc.identifier.spage13024en_US
dc.identifier.epage13035en_US
dc.identifier.eissn1520-5215-
dc.identifier.isiWOS:000296685500062-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridSadjadi, S=54407398000en_US
dc.identifier.scopusauthoridMatta, CF=7004650416en_US
dc.identifier.scopusauthoridLemke, KH=24168776600en_US
dc.identifier.scopusauthoridHamilton, IP=35317255600en_US

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