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Crystal Field Theory - Octahedral Complexes02:58

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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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An ionic compound is stable because of the electrostatic attraction between its positive and negative ions. The lattice energy of a compound is a measure of the strength of this attraction. The lattice energy (ΔHlattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid sodium chloride, the lattice energy is the enthalpy change of the process:
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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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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Related Experiment Video

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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
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Tolerance factor and phase stability of the garnet structure.

Zhen Song1, Dandan Zhou1, Quanlin Liu1

  • 1Beijing Key Laboratory for New Energy Materials and Technologies, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, People's Republic of China.

Acta Crystallographica. Section C, Structural Chemistry
|October 8, 2019
PubMed
Summary

We introduce a new structural descriptor, the tolerance factor, to predict phase stability in garnet structures. This compositional parameter, based on ionic radii, aids in understanding crystal chemistry and guiding material discovery.

Keywords:
crystal structuregarnetphase stabilitytolerance factor

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Area of Science:

  • Materials Science
  • Crystallography
  • Solid-State Chemistry

Background:

  • Garnet structures are crucial in various applications, but predicting their phase stability can be challenging.
  • Existing methods for assessing structural stability may not be universally applicable or easily calculable.
  • A need exists for a simple, compositional parameter to guide the understanding and prediction of garnet phase formation.

Purpose of the Study:

  • To introduce and define a novel structural descriptor, the tolerance factor, for garnet-type compounds.
  • To assess the utility of this tolerance factor in predicting and describing the phase stability of garnets.
  • To explore the potential application of the tolerance factor in materials design and discovery.

Main Methods:

  • The tolerance factor was defined based on the geometrical relationships between polyhedra within the garnet structure.
  • Calculation of the tolerance factor requires only ionic radius data.
  • A survey of the tolerance factor was conducted for over 130 known garnet-type compounds.

Main Results:

  • The tolerance factor was successfully introduced as a compositional parameter for garnet structures.
  • Calculations for the tolerance factor only require ionic radius information.
  • Analysis of 130 garnet compounds showed that their tolerance factor values fall within a narrow range.
  • The tolerance factor demonstrates potential for understanding garnet crystal chemistry and predicting phase stability.

Conclusions:

  • The tolerance factor is a valuable tool for the systematic description and prediction of phase stability in garnet structures.
  • This descriptor can serve as a guide for experimentalists and computational methods in identifying stable garnet phases.
  • The correlation between the tolerance factor and garnet phase stability can be leveraged in machine learning and high-throughput screening for novel material discovery.