V. N. Ikorskii | Searcharxiv

arXiv2004

Peculiarities of crystal structure of terbium (III) trifluoroacetate trihydrate

A comparative study of the crystalline and molecular structures of trifluoroacetate trihydrates of Tb(III) prepared from Tb(OH)_3 and Tb_2(CO_3)_3 by reaction with trifluoroacetic acid is made. Elemental analysis of the two reaction products in indicated them to be compounds of the same C_6H_6F_9O_9Tb. According to the X-ray structural analysis the molecular structure of the first product is described by the average statistical formula Tb_2(CF_3COO)_5(CF_3COOH)(H_2O)_5(OH) (Tb-I) and the compound is a dimer with a centre of inversion. In the second case the product is also a centrosymmetric dimer but its formula is Tb_2(CF_3COO)_6(H_2O)_6 (Tb-II). The compounds only difference is in the crystallographic positions of their hydrogen atoms. A luminescent analysis using Tb^{3+} ^5D_4-> ^7F_0 transition indicated the presence within the structure of Tb-I of the structure of Tb-II. Magnetic measurements showed that Tb-II has an antiferromagnetic ordering at low temperatures. In the case of Tb-I there also appears a ferromagnetic ordering. On the basis of the available experimental results such a behaviour was explained to be the result of some peculiar features of the hydrogen bonds in the molecules.

cond-mat.mtrl-sci↗

arXiv2004

Low-temperature anomaly in heat capacity due to overlapping the spectrums in molecular crystals

Investigations of dynamic and thermodynamic properties for a molecular crystal tris-hexafluoroacetylacetonate-iron $Fe(O_2C_5HF_6)_3$ are presented. Heat capacity $C_p(T)$ has been measured by adiabatic calorimetry method in the temperature range $4.8-321 K$. An anomaly with a maximum at $T_c = 44.6 K$ has been discovered. Intermolecular vibrations spectrum was calculated by lattice dynamics method in quasiharmonic approximation. Intramolecular frequencies are found by solving the Schrödinger equation in approach of small harmonic oscillations. In the frequency interval $\approx 30-70 cm^{-1}$ overlapping the spectrums intra- and intermolecular oscillations has been found. The good agreement for calculated and experimental $C_p(T)$ occurred to be possible for two sets of the force constants. These sets describe two phases above and below $T_c$. The difference between phases is connected with freezing of rotation $CF_3$ groups. It has been concluded that the interaction between different modes leads to phase transition and anomaly in heat capacity.

cond-mat.other↗