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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Updated: Sep 24, 2025

Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
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Crystal structure evolution in the van der Waals vanadium trihalides.

Marie Kratochvílová1, Petr Doležal1, Dávid Hovančík1

  • 1Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, 121 16 Prague 2, Czech Republic.

Journal of Physics. Condensed Matter : an Institute of Physics Journal
|May 5, 2022
PubMed
Summary

Vanadium trihalides exhibit an inverse structural transition compared to chromium trihalides, with higher symmetry in the high-temperature phase and no thermal hysteresis. This study reveals key differences in transition-metal trihalide structural behaviors.

Keywords:
first-order transitionlow-temperature x-ray diffractionsecond-order transitionstructural transitiontransition-metal trihalidevan der Waals material

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Area of Science:

  • Materials Science
  • Solid State Physics
  • Crystallography

Background:

  • Transition-metal trihalides commonly exhibit dimorphism, with distinct low-temperature (LT) and high-temperature (HT) phases.
  • Chromium trihalides (CrCl₃, CrBr₃, CrI₃) show a LT trigonal BiI₃-type structure and a HT monoclinic AlCl₃-type structure (C2/m) with significant thermal hysteresis during phase transitions.

Purpose of the Study:

  • To investigate the crystal structures and structural phase transitions of vanadium trihalides (VCl₃, VBr₃, VI₃).
  • To compare the transition behavior of vanadium trihalides with their chromium-based counterparts.
  • To explore the relationship between unit cell parameters, crystal structures, and transition types in V and Cr trihalides.

Main Methods:

  • Specific heat measurements as a function of temperature.
  • Magnetization measurements as a function of temperature.
  • X-ray diffraction analysis as a function of temperature.

Main Results:

  • Vanadium trihalides display an inverse structural transition compared to chromium trihalides, with the HT phase exhibiting higher symmetry than the LT phase.
  • Structural phase transitions in vanadium trihalides show no measurable thermal hysteresis.
  • The study discusses the evolution of the c/a ratio of unit cell parameters and its relation to structural types and transition nature.

Conclusions:

  • Vanadium trihalides present a contrasting structural phase transition mechanism to chromium trihalides.
  • The absence of hysteresis in vanadium trihalides suggests a different phase transition pathway.
  • Understanding these differences provides insights into the broader trends in transition-metal trihalide behavior.