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DFT and Metal-Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?

Petrie, Simon; Stranger, Robert

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Density functional theory (DFT) calculations are reported for 16 binuclear transition-metal complexes. Structural motifs studied include face-shared and edge-shared bioctahedra, carboxylate-bridged "paddlewheel" complexes, and nonbridged dimers possessing direct metal-metal bonds. Most of these structure types are represented both by multiply charged (tri- and tetra-anionic, and tetracationic) and by neutral or singly charged examples. Geometry optimizations for these species, in the vacuum...[Show more]

dc.contributor.authorPetrie, Simon
dc.contributor.authorStranger, Robert
dc.date.accessioned2015-12-13T23:10:03Z
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/1885/87280
dc.description.abstractDensity functional theory (DFT) calculations are reported for 16 binuclear transition-metal complexes. Structural motifs studied include face-shared and edge-shared bioctahedra, carboxylate-bridged "paddlewheel" complexes, and nonbridged dimers possessing direct metal-metal bonds. Most of these structure types are represented both by multiply charged (tri- and tetra-anionic, and tetracationic) and by neutral or singly charged examples. Geometry optimizations for these species, in the vacuum phase, use the "broken-symmetry" approach coupled with nine different DFT methods. We find a clear dichotomy in the performance of different DFT approaches. For the eight neutral or singly charged complexes, orthodox gradient-corrected DFT methods such as BP and PBE perform generally very well in reproducing in vacuo the complex geometries obtained from X-ray crystallographic studies. In contrast, these orthodox approaches fail to reliably mimic the crystalline geometries for more highly charged complexes such as Mo2Cl93-, Cr2(CH3)84-, and Rh2(NCCH3)104+. Much closer agreement with experimental condensed-phase structures for the multiply charged dinuclear complexes is seen for two " local-density-approximation" approaches, Xα and VWN, and for VWN+B-LYP, an unorthodox combination of the VWN local and B-LYP nonlocal density functionals. The very good performance of the latter approaches arises from an essentially fortuitous cancellation of errors: while the generally overbinding nature of these approaches suggests that they will not reliably describe true gas-phase structures, this overbinding compensates very well for the coulombic distortion expected when complexes are removed from the charge-stabilizing environment of the crystalline or solvated state. We recommend that, as an alternative to the (computationally expensive) incorporation of solvent-field corrections, VWN+B-LYP is the preferred method for structural characterization of triply or more highly charged dinuclear complexes, while orthodox approaches such as PBE perform best for neutral or mildly charged complexes.
dc.publisherAmerican Chemical Society
dc.sourceInorganic Chemistry
dc.subjectKeywords: metal complex; transition element; article; chemical bond; chemical interaction; chemical structure; complex formation; crystallization; density functional theory; mathematical analysis; phase transition; structure analysis; X ray crystallography
dc.titleDFT and Metal-Metal Bonding: A Dys-Functional Treatment for Multiply Charged Complexes?
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
local.identifier.citationvolume43
dc.date.issued2004
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationMigratedxPub16504
local.type.statusPublished Version
local.contributor.affiliationPetrie, Simon, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationStranger, Robert, College of Physical and Mathematical Sciences, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.issue8
local.bibliographicCitation.startpage2597
local.bibliographicCitation.lastpage2610
local.identifier.doi10.1021/ic034525e
dc.date.updated2015-12-12T08:22:13Z
local.identifier.scopusID2-s2.0-4043107344
CollectionsANU Research Publications

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