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 Title: Pressure Tuning of the Electronic Spectra of Quasi-One-Dimensional Mixed Valence Semiconductors Author(s): Stroud, Mary Ann Doctoral Committee Chair(s): Drickamer, Harry G., Department / Program: Chemical Engineering Discipline: Chemical Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Inorganic Engineering, Materials Science Abstract: The effects of high pressure on the electronic spectra of the mixed valence semiconductors, K$\sb4$(Pt$\sb2$(P$\sb2$O$\sb5$H$\sb2)\sb4$X) $\cdot$3H$\sb2$O; X = Cl, Br were investigated to 10.0 GPa. Their electronic spectra consist of transitions seen in the reduced salt, K$\sb4$(Pt$\sb2$(P$\sb2$O$\sb5$H$\sb2)\sb4$) $\cdot$2H$\sb2$O, and the oxidized salt, K$\sb4$(Pt$\sb2$(P$\sb2$O$\sb5$H$\sb2)\sb4$Cl$\sb2$) $\cdot$2H$\sb2$O, modified to some extent, along with an intervalence charge transfer (IVCT) band characteristic of the mixed valence complex itself. The reduced salt and the oxidized salt have also been studied so that direct comparison with the monohalide could be made. For all four complexes, two first order effects controlled the pressure-induced shifts on the energy of the electronic transitions. These effects, which are discussed in terms of simplified molecular orbital diagrams, are pressure-induced changes in the ligand field splitting in the molecule and an increase in the splitting between the bonding and anti-bonding orbitals within a manifold.In addition, in the mixed valence complexes the IVCT band yielded information about the structural changes that occurred with increasing pressure. In both complexes, the energy of the IVCT band shifted sharply to lower energy as pressure was increased to 4.0 GPa and then leveled off. This result is consistent with a decrease in the Peierls distortion with increasing pressure. Issue Date: 1988 Type: Text Description: 124 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988. URI: http://hdl.handle.net/2142/69793 Other Identifier(s): (UMI)AAI8823261 Date Available in IDEALS: 2014-12-15 Date Deposited: 1988
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