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High-pressure Raman spectroscopy of transition metal cyanides

Moritomo, Yutaka*; Matsuda, Tomoyuki*; Fuchikawa, Ryota*; Abe, Yuta  ; Kamioka, Hayato*

Prussian blue lattice is known to show characteristic thermal response; coefficient($$beta$$ $$equiv$$ $$frac{d{it a}}{d{it T}}$$;${it a}$ is lattice constant) of the thermal expansion changes the sign from positive to negative with increase in ${it a}$. In order to comprehend the curious thermal response, we systematically investigated pressure-response of lattice for ${it A$_{x}$}$${it M$^{2+}$}$[Fe$$^{3+}$$(CN)$$_{6}$$]$$_{it y}$$${it z}$H$$_{2}$$O (${it A}$= Rb and Cs, M = Ni, Zn and Cd) by means of high-pressure Raman spectroscopy. We found that pressure coefficients ($$alpha$$ $$equiv$$ ${it d}$ $$hbar$$$$omega$$/${it dP}$ of the Raman shift ($$hbar$$$$omega$$) for the CN stretching modes are fairly suppressed in the $$M$$ = Cd compounds. The suppression of $$alpha$$ is interpreted in terms of the enhance rotational instability of the Fe(CN)$$_{6}$$ octahedra in the large-a region.

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Category:Physics, Multidisciplinary

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