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What are octahedral, tetrahedral, and square planar crystal fields?

These terms describe the arrangement of ligands around a central metal ion in Crystal Field Theory (CFT) and how that arrangement causes the splitting of the metal’s d-orbitals.


1. Octahedral Crystal Field

  • Arrangement: Six ligands placed symmetrically around the metal, along the x, y, and z axes (like at the corners of an octahedron).
  • Effect on d-orbitals:
    • Orbitals pointing directly at the ligands (along axes) feel strong repulsion → go higher in energy.
    • Orbitals pointing between ligands feel less repulsion → stay lower in energy.
  • Common in: Transition metal complexes like [Fe(H₂O)₆]²⁺.
  • Properties: Can be high-spin or low-spin depending on ligand strength.

2. Tetrahedral Crystal Field

  • Arrangement: Four ligands placed between the axes, at the corners of a tetrahedron.
  • Effect on d-orbitals:
    • Orbitals pointing between axes feel stronger repulsion → higher in energy.
    • Orbitals pointing along axes feel less repulsion → lower in energy.
  • Key difference: Splitting pattern is opposite to octahedral and the energy gap is smaller.
  • Common in: Complexes like [CoCl₄]²⁻.
  • Properties: Usually high-spin because the energy gap is small.

3. Square Planar Crystal Field

  • Arrangement: Four ligands placed in one flat plane, along the x and y axes.
  • Effect on d-orbitals:
    • The orbital lying in the plane and pointing directly at ligands rises very high in energy.
    • The other orbitals are pushed less, depending on how they align with ligands.
  • Common in: d⁸ metals like Ni²⁺, Pd²⁺, Pt²⁺.
  • Properties: Strong splitting, usually low-spin and diamagnetic.

In short:

  • Octahedral (6 ligands): 2 groups of orbitals, large splitting.
  • Tetrahedral (4 ligands): Opposite splitting pattern, smaller gap.
  • Square planar (4 ligands in a plane): One orbital much higher, leading to strong preference for certain electron arrangements.

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