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Analysis of Far-Infrared Spectra of Antiferromagnetic FeC<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>

G. A. PrinzNaval Research Laboratory, Washington, D. C. 20375D. W. ForesterNaval Research Laboratory, Washington, D. C. 20375John L. LewisNaval Research Laboratory, Washington, D. C. 20375
1973lv
ABI

Abstract

The transmission spectrum of antiferromagnetic FeC${\mathrm{O}}_{3}$ has been investigated in the far-infrared region from 20 to 300 ${\mathrm{cm}}^{\ensuremath{-}1}$, for temperatures from 4.2 to 70 K and in applied fields up to 90 kOe. Spectra were obtained from natural single crystals and high-purity synthetic powders. At 4.2 K, a sharp electronic transition (magnetic dipole) was observed at 112.5 ${\mathrm{cm}}^{\ensuremath{-}1}$, exhibiting parallel and perpendicular splitting factors of 6.6 and O, respectively. Its oscillator strength is $f=2.1\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}8}$. An additional weak electronic line is observed at 160 ${\mathrm{cm}}^{\ensuremath{-}1}$. The details of these transitions and electronic Raman transitions observed by others are successfully described by the ${\mathrm{Fe}}^{2+}$ single-ion Hamilitonian $\mathcal{H}=R\ensuremath{\lambda}\stackrel{\ensuremath{\rightarrow}}{\mathrm{L}}\ifmmode\cdot\else\textperiodcentered\fi{}\stackrel{\ensuremath{\rightarrow}}{\mathrm{S}}+{R}^{2}\ensuremath{\zeta}({L}_{z}^{2}\ensuremath{-}\frac{2}{3})+\mathcal{J}{S}_{z}$, where $\ensuremath{\lambda}$, $\ensuremath{\zeta}$, and $\mathcal{J}$ are the spin-orbit, trigonal-field, and Ising-molecular-field parameters, respectively, and $R$ is an "orbital-reduction" factor. The analysis yields values for these parameters of $R\ensuremath{\lambda}=105$ ${\mathrm{cm}}^{\ensuremath{-}1}$, $\ensuremath{-}{R}^{2}\ensuremath{\zeta}=1506$ ${\mathrm{cm}}^{\ensuremath{-}1}$, $R\ensuremath{\approx}1$, and $\mathcal{J}=19$ ${\mathrm{cm}}^{\ensuremath{-}1}$. The observed far-infrared transitions are identified as being within the low $^{5}E$ spin-orbit manifold from the ground state (${M}_{J}=\ensuremath{-}1$) to the two components of the ${M}_{J}=0$ doublet. The temperature dependence of the 112.5-${\mathrm{cm}}^{\ensuremath{-}1}$ transition is studied from 4.2 to 70 K, and its intensity is observed to drop sharply as the temperature is raised to the vicinity of ${T}_{N}=38.4$ K. This behavior is compared to that of an Ising spin system. In addition, three phonons are observed at 186, 201, and 224 ${\mathrm{cm}}^{\ensuremath{-}1}$ and are identified as external ${E}_{u}$, ${A}_{2u}$, and ${E}_{u}$ modes, respectively.

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