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Drickamer, Harry G., Stroud, Mary Ann 2014-12-15T19:54:43Z 2014-12-15T19:54:43Z 10000-01-01 1988 1988 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. Made available in DSpace on 2014-12-15T19:54:43Z (GMT). No. of bitstreams: 1 8823261.pdf: 3746218 bytes, checksum: 83f8ac3a6579144f34b8b28aff987b18 (MD5) Previous issue date: 1988 Embargo set by: Seth Robbins for item 69959 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs U of I Only 124 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988. http://hdl.handle.net/2142/69793 (UMI)AAI8823261 Chemistry, Inorganic Engineering, Materials Science Pressure Tuning of the Electronic Spectra of Quasi-One-Dimensional Mixed Valence Semiconductors text Chemical Engineering Chemical Engineering University of Illinois at Urbana-Champaign Dissertation Ph.D.