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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.
CFT focuses on...
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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.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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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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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...
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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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Tuning Oxide Properties by Oxygen Vacancy Control During Growth and Annealing
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Massive band gap variation in layered oxides through cation ordering.

Prasanna V Balachandran1, James M Rondinelli2

  • 1Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.

Nature Communications
|January 31, 2015
PubMed
Summary

Researchers achieved significant electronic band gap tuning in LaSrAlO4 oxide by ordering charged planes, leading to up to 200% band gap changes without altering composition. This offers new possibilities for electronic structure engineering in complex oxides.

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Area of Science:

  • Materials Science
  • Solid State Physics
  • Oxide Electronics

Background:

  • The electronic band gap is crucial for optoelectronic applications like photovoltaics and lasers.
  • Conventional methods for band gap tuning (alloying, strain) have limitations in spectral variation and material modification.

Purpose of the Study:

  • To demonstrate large, composition-independent band gap tuning in LaSrAlO4.
  • To explore a novel mechanism for electronic structure engineering in layered oxides.

Main Methods:

  • First-principles calculations.
  • Analysis of atomic ordering and internal electric fields in Ruddlesden-Popper oxides.

Main Results:

  • Achieved up to 200% (approx. 2 eV) band gap changes in LaSrAlO4 without chemical or strain modification.
  • Identified internal electric fields generated by ordered [LaO](1+) and [SrO](0) planes.
  • Correlated electric fields with local atomic displacements and bond distortions controlling band edges.

Conclusions:

  • Plane ordering in layered oxides provides a powerful route for substantial electronic band gap engineering.
  • This method enables precise control over electronic properties without altering material composition, advancing complex oxide applications.