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

Dick, Andrew, Rahemi, Hedayat, Krausz, Elmars R, Hanson, Graeme R. and Riley, Mark J. (2008) The highly resolved electronic spectrum of the square planar CuCl42- ion. Journal of Chemical Physics, 129 21 Article # 214505: . doi:10.1063/1.3033367

Attached Files (Some files may be inaccessible until you login with your UQ eSpace credentials)
Name Description MIMEType Size Downloads
UQ170709_OA.pdf Full text (open access) application/pdf 607.94KB 0

Author Dick, Andrew
Rahemi, Hedayat
Krausz, Elmars R
Hanson, Graeme R.
Riley, Mark J.
Title The highly resolved electronic spectrum of the square planar CuCl42- ion
Formatted title
The highly resolved electronic spectrum of the square planar CuCl42- ion
Journal name Journal of Chemical Physics   Check publisher's open access policy
ISSN 0021-9606
Publication date 2008-12-07
Year available 2008
Sub-type Article (original research)
DOI 10.1063/1.3033367
Open Access Status File (Publisher version)
Volume 129
Issue 21 Article # 214505
Total pages 8
Place of publication Melville, New York, United States
Publisher American Institute of Physics
Language eng
Subject C1
030299 Inorganic Chemistry not elsewhere classified
970103 Expanding Knowledge in the Chemical Sciences
Abstract The low temperature magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectra of Cu(II) doped Cs(2)ZrCl(6) are reported. The Cu(II) ion is incorporated as the square planar copper tetrachloride ion, CuCl(4)2-, which substitutes at the Zr(IV) site in the Cs(2)ZrCl(6) 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 (2)B(1g)(x(2)-y(2))->(2)B(2g)(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 (2)E(g)(xz,yz) excited state allows this splitting to be determined for the first time. Accurate and unambiguous spectral parameters for the CuCl(4)2- ion are important as it has become a benchmark transition metal complex for theoretical electronic structure calculations.
Formatted abstract
The low temperature magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectra of Cu(II) doped Cs2ZrCl6 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. ©2008 American Institute of Physics
Keyword caesium compounds
copper
density functional theory
excited states
Franck-Condon factors
hyperfine interactions
infrared spectra
magnetic circular dichroism
magnetic moments
paramagnetic resonance
zirconium compounds
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published 5 December 2008

Document type: Journal Article
Sub-type: Article (original research)
Collections: 2009 Higher Education Research Data Collection
School of Chemistry and Molecular Biosciences
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 4 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 2 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Thu, 19 Mar 2009, 00:45:44 EST by Jennifer Falknau on behalf of School of Chemistry & Molecular Biosciences