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Specific heat measurements constitute one of the most powerful experimental methods to probe fundamental excitations in solids. After the proposition of Einsteins model, more than one century ago (Annalen der Physik textbf{22}, 180 (1907)), several t heoretical models have been proposed to describe experimental results. Here we report on a detailed analysis of the two-peak specific heat anomalies observed in several materials. Employing a simple multilevel model, varying the spacing between the energy levels $Delta_i$ = $(E_i$ $-$ $E_{0})$ and the degeneracy of each energy level $g_i$, we derive the required conditions for the appearance of such anomalies. Our findings indicate that a ratio of $Delta_2$/$Delta_1$ $thickapprox$ 10 between the energy levels and a high degeneracy of one of the energy levels define the two-peaks regime in the specific heat. Our approach accurately matches recent experimental results. Furthermore, using a mean-field approach we calculate the specific heat of a degenerate Schottky-like system undergoing a ferromagnetic (FM) phase transition. Our results reveal that as the degeneracy is increased the Schottky maximum in the specific heat becomes narrow while the peak associated with the FM transition remains unaffected.
Charge-ordering phenomena have been highly topical over the last few years. A phase transition towards a charge ordered state has been observed experimentally in several classes of materials. Among them, many studies have been devoted to the family o f quasi-one dimensional organic charge-transfer salts (TMTTF)$_2$X, where (TMTTF) stands for tetramethyltetrathiafulvalene and X for a monovalent anion (X = PF$_6$, AsF$_6$ and SbF$_6$). However, the relationship between the electron localization phenomena and the role of the lattice distortion in stabilizing the charge-ordering pattern is poorly documented in the literature. Here we present a brief overview of selected literature results with emphasis placed on recent thermal expansion experiments probing the charge-ordering transition of these salts.
We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF)$_2$PF$_6$ and (TMTSF)$_2$AsF$_6$ (TMTSF : tetramethyl-tetraselenafulvalene). The 4 K neutron scattering structure refinement of the fully deuterated (TMTSF)$_2$PF$_6$-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)$_2$PF$_6$-H12 salt previously determined at the same temperature. Surprisingly it is found that deuteration corresponds to the application of a negative pressure of 5 x 10$^2$ MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF$_6$ and AsF$_6$ salts. Two different thermal behaviors have been distinguished. Low-Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies {theta}$_E$ = 8.3 K and {theta}$_E$ = 6.7 K for the PF$_6$-D12 and AsF$_6$-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large-Bragg-angle measurements evidence an unexpected structural change around 55 K which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)$_2$PF$_6$ is dominated by the librational motion of the PF$_6$ units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: {theta}$_E$ = 50 K and {theta}$_E$ = 76 K for the PF$_6$-D12 and PF$_6$-H12 salts, respectively.
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