- Language(s)
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English
- Published
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1986.
- Summary
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The results reported in this thesis demonstrate the effectiveness with which intercalation chemistry can be studied. (Abstract shortened with permission of author.)
FTIR spectra of Cd(,2)P(,2)S(,6), Cd(,2)P(,2)Se(,6), Mn(,2)P(,2)S(,6), Fe(,2)P(,2)S(,6), and Co(,2)P(,2)S(,6) reveal that, in the iron and cobalt lattices, the trigonal distortion about the metal ion results in an electronic absorption at 1800 cm('-1) and 1200 cm('-1) respectively. Intercalating n-propylamine into Fe(,2)P(,2)S(,6) shifts this transition to higher energy.
The room temperature intercalation of Cd(,2)P(,2)S(,6) by a pyridine solution of Fe('+3) results in the formation of a highly colored blue species within the van der Waals gap of the lattice that has tentatively been assigned to S(,8)('+2). Mass spectrometry of the thermal deintercalation products suggests the presence of 4,4'-bipyridine also within the van der Waals gap. The intercalation mechanism of Fe('+3)/pyridine is found to be different than the intercalation mechanism of wet pyridine.
The orientation and oxidation state of cobaltocene, Co(C(,5)H(,5))(,2), as an intercalant in Cd(,2)P(,2)S(,6) is determined from ESR and optical measurements. Results are in conflict with those previously published.
Photoluminescence and photoluminescence excitation spectra of Cd(,2)P(,2)S(,6), Cd(,2)P(,2)Se(,6), Mn(,2)P(,2)S(,6), Zn(,2)P(,2)S(,6), and Cd(,2)P(,2)S(,6)(pyridine) are reported. The similarity between the optical properties of these compounds and GaS and GaSe is demonstrated.
From ESR spectra of Cd(,2)P(,2)Se(,6)-1%Mn(II), where the Mn(II) occupy Cd(II) sites, the conclusion is that the metal ion resides in a large axial field. The connection between this observation and the two dimensional nature of the material is discussed.
region is known as intercalation. In this work, the properties of pure M(,2)P(,2)X(,6) lattices and the perturbation of these properties upon intercalation are investigated using ESR, optical, and FTIR techniques.
The transition metal phosphorus chalcogenides (M(,2)P(,2)X(,6), where M is a divalent transition metal ion and X is a sulphur or selenium) crystallize in a layered structure where layers of transition metal ions are separated by two layers of chalcogenide atoms. Covalently bonded phosphorus, as P(,2), occupies 1/3 of the metal ion sites. The gap between chalcogenide layers, referred to as the van der Waals gap, is a region accessible to atoms, molecules, and ions. The insertion of such species into this
- Physical Description
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153 p.