Crystal structure evolution in the van der Waals vanadium trihalides. 2022

Marie Kratochvílová, and Petr Doležal, and Dávid Hovančík, and Jiří Pospíšil, and Anežka Bendová, and Michal Dušek, and Václav Holý, and Vladimír Sechovský
Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 Prague 2, Czech Republic.

Most transition-metal trihalides are dimorphic. The representative chromium-based triad, CrCl3, CrBr3, CrI3, is characterized by the low-temperature (LT) phase adopting the trigonal BiI3-type while the structure of the high-temperature (HT) phase is monoclinic of AlCl3type (C2/m). The structural transition between the two crystallographic phases is of the first-order type with large thermal hysteresis in CrCl3and CrI3. We studied crystal structures and structural phase transitions of vanadium-based counterparts VCl3, VBr3, and VI3by measuring specific heat, magnetization, and x-ray diffraction as functions of temperature and observed an inverse situation. In these cases, the HT phase has a higher symmetry while the LT structure reveals a lower symmetry. The structural phase transition between them shows no measurable hysteresis in contrast to CrX3. Possible relations of the evolution of the ratioc/aof the unit cell parameters, types of crystal structures, and nature of the structural transitions in V and Cr trihalides are discussed.

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