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Rigid covalent bond of α-Sulfur investigated via temperature-dependent EXAFS.
This study performs extended X-ray absorption fine structure (EXAFS) measurements for the S-K edge in the temperature range of 10 and 300 K in the transmission mode using a photodiode to detect the transmitted X-rays. It provides the first report of temperature variations in the structural parameters of α-S. As the temperature increases from 10 to 300 K in the Fourier transform of kχ(k), the first peak corresponding to the covalent bond of the eight-membered ring becomes slightly low anomalously despite thermal disturbances. However, as in normal materials, the second peak at 300 K decreases to approximately half of that at 10 K, which contains several intra- and inter-ring correlations. All structural parameters of the covalent bond obtained by nonlinear least squares fitting exhibit missing temperature variations. A value of zero for the asymmetric parameter in the EXAFS (C3) implies that the potential of the covalent bond is symmetric, and the constant value of the mean square relative displacement (MSRD) with temperature implies that the potential is extremely high. The Einstein model fitting for the temperature variation in the MSRD yields an Einstein temperature of 942 K and force constant (K) of 405 N/m. The value of K is the largest among those of chalcogen elements.
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