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The highly resolved electronic spectrum of the square planar CuCl₄²⁻ ion

Dick, Andrew; Rahemi, Hedayat; Krausz, Elmars; Hanson, Graeme R.; Riley, Mark J.

Description

The low temperature magnetic circular dichroism(MCD) and electron paramagnetic resonance(EPR)spectra of Cu(II) dopedCs₂ZrCl₆ are reported. The Cu(II) ion is incorporated as the square planar copper tetrachloride ion, CuCl₄²⁻, which substitutes at the Zr(IV) site in the Cs₂ZrCl₆ lattice, with a complete absence of axial coordination. Both the EPR and MCD show highly resolved spectra from which it is possible to determine the superhyperfine coupling constants and excited state geometries...[Show more]

dc.contributor.authorDick, Andrew
dc.contributor.authorRahemi, Hedayat
dc.contributor.authorKrausz, Elmars
dc.contributor.authorHanson, Graeme R.
dc.contributor.authorRiley, Mark J.
dc.date.accessioned2015-11-25T01:07:57Z
dc.date.available2015-11-25T01:07:57Z
dc.identifier.issn0021-9606
dc.identifier.urihttp://hdl.handle.net/1885/16731
dc.description.abstractThe low temperature magnetic circular dichroism(MCD) and electron paramagnetic resonance(EPR)spectra of Cu(II) dopedCs₂ZrCl₆ are reported. The Cu(II) ion is incorporated as the square planar copper tetrachloride ion, CuCl₄²⁻, which substitutes at the Zr(IV) site in the Cs₂ZrCl₆ lattice, with a complete absence of axial coordination. Both the EPR and MCD show highly resolved spectra from which it is possible to determine the superhyperfine coupling constants and excited state geometries respectively. The Franck–Condon intensity patterns suggest that there is a substantial relaxation of the host lattice about the impurity ion. For the lowest energy ²B1g(x²-y²)→²B2g(xy) transition, both the magnetic dipole allowed electronic origin as well as vibronic false origins are observed. The high resolution of the spectra allowed the accurate determination of the odd parity vibrations that are active in the spectra. The opposite sign of the MCD of the two components of the ²Eg(xz,yz)excited state allows this splitting to be determined for the first time. Accurate and unambiguous spectral parameters for the CuCl₄²⁻ ion are important as it has become a benchmark transition metal complex for theoretical electronic structure calculations.
dc.publisherAmerican Institute of Physics (AIP)
dc.rightshttp://www.sherpa.ac.uk/romeo/issn/0021-9606..."Publishers version/PDF may be used on author's personal website, institutional website or institutional repository" from SHERPA/RoMEO site (as at 25/11/15). Copyright 2008 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics and may be found at https://doi.org/10.1063/1.3033367
dc.sourceThe Journal of Chemical Physics
dc.subjectabsorption
dc.subjectcalibration
dc.subjectcircular dichroism
dc.subjectcopper
dc.subjectelectron spin resonance spectroscopy
dc.subjectligands
dc.subjectmagnetics
dc.subjectsensitivity and specificity
dc.subjecttemperature
dc.subjectelectrons
dc.titleThe highly resolved electronic spectrum of the square planar CuCl₄²⁻ ion
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume129
dc.date.issued2008-12-05
local.identifier.absfor029901
local.identifier.ariespublicationu4217927xPUB312
local.publisher.urlhttps://www.aip.org/
local.type.statusPublished Version
local.contributor.affiliationDick, Andrew, University of Queensland, Australia
local.contributor.affiliationRahemi, Hedayat, Urmia University, Iran
local.contributor.affiliationKrausz, Elmars, College of Physical and Mathematical Sciences, CPMS Research School of Chemistry, RSC General, The Australian National University
local.contributor.affiliationHanson, Graeme, University of Queensland, Australia
local.contributor.affiliationRiley, Mark J, University of Queensland, Australia
local.identifier.essn1089-7690
local.bibliographicCitation.issue21
local.bibliographicCitation.startpage214505
local.bibliographicCitation.lastpage8
local.identifier.doi10.1063/1.3033367
dc.date.updated2015-12-09T09:55:34Z
local.identifier.scopusID2-s2.0-57349190708
local.identifier.thomsonID000261430900031
CollectionsANU Research Publications

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