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d(3,7) non-cubic ligand field spectrum and the electronic spectra of quadrate chromium (III) complexes

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Date Issued:
2005
Summary:
In the first-part of this two-part study, the quadrate energy levels of the d3 configuration including spin-orbit interaction are derived in the rare-earth coupling scheme using ligand-field symmetry parameters Dq, Ds, and Dt, by the method of tensor-operators. Comparison is made to the strong field coupling scheme. In the second part of this study, interpretation of polarised single-crystal spectra of trans-[Cr(tmd)2F2]ClO4, trans-[Cr(en)2(dma)2](ClO4) 3, trans-[Cr(en)2(dmf)Br](ClO4) 2 and trans-[Cr(en)2(dmf)Cl](ClO4) 2 as well as unpolarised single-crystal spectrum of trans-[Cr(en) 2(dmf)2](ClO4)3 and solution spectra of trans-[Cr(pn)(en)F2]ClO4, trans-[Cr(en)2FCl]ClO4 and trans-[Cr(en) 2FBr]ClO4 is made using Gaussian analysis of the bands in both polarisations where possible. Ligand field parameters Dq, Ds, Dt and B are extracted from the spectra using energy matrices in the strong-field coupling scheme by fitting the quadrate components of the two lowest energy cubic quartet bands exactly. Discussion of these parameters and the translated AOM (angular overlap model) parameters, is presented. A thorough interpretation of the high-energy intraconfigurational doublet bands in a number of trans-diacidobis (ethylenediamine) chromium (111) complexes is made using quadrate energy matrices including spin-orbit interaction. Entire programming code for the energy matrices in the rare-earth coupling scheme is included, as are procedures for computing 3-j and 6-j symbols. The complete quadrate energy matrices for d3 configuration in the strong-field coupling scheme with spin-orbit perturbation as well quadrate energy matrices for d3 configuration in the rare-earth coupling scheme are included.
Title: The d(3,7) non-cubic ligand field spectrum and the electronic spectra of quadrate chromium (III) complexes.
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Name(s): Williams, Chamindra S.
Florida Atlantic University, Degree Grantor
Charles E. Schmidt College of Science
Department of Chemistry and Biochemistry
Type of Resource: text
Genre: Electronic Thesis Or Dissertation
Issuance: monographic
Date Issued: 2005
Publisher: Florida Atlantic University
Place of Publication: Boca Raton, Fla.
Physical Form: application/pdf
Extent: 167 p.
Language(s): English
Summary: In the first-part of this two-part study, the quadrate energy levels of the d3 configuration including spin-orbit interaction are derived in the rare-earth coupling scheme using ligand-field symmetry parameters Dq, Ds, and Dt, by the method of tensor-operators. Comparison is made to the strong field coupling scheme. In the second part of this study, interpretation of polarised single-crystal spectra of trans-[Cr(tmd)2F2]ClO4, trans-[Cr(en)2(dma)2](ClO4) 3, trans-[Cr(en)2(dmf)Br](ClO4) 2 and trans-[Cr(en)2(dmf)Cl](ClO4) 2 as well as unpolarised single-crystal spectrum of trans-[Cr(en) 2(dmf)2](ClO4)3 and solution spectra of trans-[Cr(pn)(en)F2]ClO4, trans-[Cr(en)2FCl]ClO4 and trans-[Cr(en) 2FBr]ClO4 is made using Gaussian analysis of the bands in both polarisations where possible. Ligand field parameters Dq, Ds, Dt and B are extracted from the spectra using energy matrices in the strong-field coupling scheme by fitting the quadrate components of the two lowest energy cubic quartet bands exactly. Discussion of these parameters and the translated AOM (angular overlap model) parameters, is presented. A thorough interpretation of the high-energy intraconfigurational doublet bands in a number of trans-diacidobis (ethylenediamine) chromium (111) complexes is made using quadrate energy matrices including spin-orbit interaction. Entire programming code for the energy matrices in the rare-earth coupling scheme is included, as are procedures for computing 3-j and 6-j symbols. The complete quadrate energy matrices for d3 configuration in the strong-field coupling scheme with spin-orbit perturbation as well quadrate energy matrices for d3 configuration in the rare-earth coupling scheme are included.
Identifier: 9780542384899 (isbn), 12180 (digitool), FADT12180 (IID), fau:9087 (fedora)
Collection: FAU Electronic Theses and Dissertations Collection
Note(s): Adviser: J. R. Perumareddi.
Thesis (Ph.D.)--Florida Atlantic University, 2005.
Subject(s): Chemistry, Inorganic
Chemistry, Physical
Held by: Florida Atlantic University Libraries
Persistent Link to This Record: http://purl.flvc.org/fcla/dt/12180
Sublocation: Digital Library
Use and Reproduction: Copyright © is held by the author, with permission granted to Florida Atlantic University to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Use and Reproduction: http://rightsstatements.org/vocab/InC/1.0/
Owner Institution: FAU
Is Part of Series: Florida Atlantic University Digital Library Collections.