Skip navigation
Skip navigation

Quantifying the Effect of High-Spin/low-spin Crossover on Electron Delocalization in d 5 d 5 M 2 Cl 9 3- (M = Fe, Ru, Os) dimers

Stranger, Robert; Lovell, Timothy; McGrady, John Ewart

Description

Density functional theory has been used to investigate the effect of high-spin/low-spin crossover on the delocalization of metal-based electrons in homo- and hetero-bimetallic d5d5 face-shared M2Cl93- (M = Fe, Ru, Os) dimers. The energetic contributions of the ligand-field, ΔELF, spin-polarization, ΔEspe, and orbital overlap, ΔEovlp, terms to the high-spin/low-spin and localized/delocalized equilibria in these dimer systems have been quantified. The two equilibria are found to exhibit a strong...[Show more]

dc.contributor.authorStranger, Robert
dc.contributor.authorLovell, Timothy
dc.contributor.authorMcGrady, John Ewart
dc.date.accessioned2015-12-13T23:05:52Z
dc.identifier.issn0277-5387
dc.identifier.urihttp://hdl.handle.net/1885/85748
dc.description.abstractDensity functional theory has been used to investigate the effect of high-spin/low-spin crossover on the delocalization of metal-based electrons in homo- and hetero-bimetallic d5d5 face-shared M2Cl93- (M = Fe, Ru, Os) dimers. The energetic contributions of the ligand-field, ΔELF, spin-polarization, ΔEspe, and orbital overlap, ΔEovlp, terms to the high-spin/low-spin and localized/delocalized equilibria in these dimer systems have been quantified. The two equilibria are found to exhibit a strong linear dependence, which can be attributed to their connection with the single-ion spin-polarization energy. It can be concluded that metal-metal bond formation necessitates a crossover from a high-spin to low-spin configuration in these dimer systems, and, therefore, neither delocalized high-spin or localized low-spin d5d5 structures are likely to occur.
dc.publisherPergamon-Elsevier Ltd
dc.sourcePolyhedron
dc.subjectKeywords: chloride; dimer; iron derivative; osmium derivative; ruthenium derivative; article; calculation; chemical analysis; complex formation; density; density functional theory; electron; energy transfer; polarization; quantitative analysis; theory Antiferromagnetic coupling; Broken-symmetry; Density functional theory; Electron delocalization; Face-shared dimers; High-spin/low-spin crossover; Metal-metal bonding
dc.titleQuantifying the Effect of High-Spin/low-spin Crossover on Electron Delocalization in d 5 d 5 M 2 Cl 9 3- (M = Fe, Ru, Os) dimers
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
local.identifier.citationvolume21
dc.date.issued2002
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationMigratedxPub14391
local.type.statusPublished Version
local.contributor.affiliationStranger, Robert, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationLovell, Timothy, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationMcGrady, John Ewart, University of York
local.description.embargo2037-12-31
local.bibliographicCitation.startpage1969
local.bibliographicCitation.lastpage1977
local.identifier.doi10.1016/S0277-5387(02)01105-1
dc.date.updated2015-12-12T08:02:40Z
local.identifier.scopusID2-s2.0-0036715447
CollectionsANU Research Publications

Download

File Description SizeFormat Image
01_Stranger_Quantifying_the_Effect_of_2002.pdf384.86 kBAdobe PDF    Request a copy
02_Stranger_Quantifying_the_Effect_of_2002.pdf384.86 kBAdobe PDF    Request a copy


Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  19 May 2020/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator