The room-temperature reststrahlen spectra of flame fusion grown NiO and CoO, as well as those of three intermediate members of this solid solution series, are presented. A full Kramers-Kronig analysis on all members has been performed and checked with damped oscillator calculations. The resulting refractive indices, extinction coefficients, dielectric constants, effective ionic charges (Szigeti q*), and characteristic frequencies are presented along with the lattice constants and are discussed in the light of their interrelation.
The far infrared spectra of the copper halides CuCl, CuBr, and Cul have been measured in transmission and in reflection at various fixed temperatures from room temperature to liquid-helium temperature. Marked changes of such parameters as resonance frquency and damping as a function of temperature have been observed, also a line-splitting in the case of CuCl. In addition, a considerable increase in the asymmetry of the transmission curves with decreasing temperature has been observed.
Anomalous thermal expansion is treated through an analytical approach, based on the anharmonic behavior of lattice vibrations of the solids CuCl and CuBr of which complete ir spectroscopic data were available for the low temperature region. In the two cases examined here, anomalous thermal expansion as well as change of anharmonic factor, as a function of temperature, show a mirrorlike proportionality. In addition, drastic changes of ir energy absorption take place within the temperature region of reexpansion, suggesting a substantial increase of the ionic fraction of binding, coupled with a corresponding decrease of the covalent fraction, within the re-expansion period. These striking events appear to be the basic reason for the re-expansion phenomenon, since the sum value of the ionic radii of the compounds in question is greater than the sum value of the covalent radii, thus enlarging the interatomic distance, instead of contracting it.
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