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Q5.16:
Draw figure to show the splitting of d orbitals in an octahedral crystal field.

Solution :

Theoretical Foundation: Crystal Field Theory (CFT)

In an isolated transition metal ion, all five $d$-orbitals ($d_{xy}$, $d_{yz}$, $d_{zx}$, $d_{x^2-y^2}$, and $d_{z^2}$) are degenerate, meaning they possess identical energy. When six ligands approach the metal ion in an octahedral arrangement along the Cartesian axes ($x, y, z$), the electrostatic field causes the degeneracy to split. Orbitals pointing directly at the ligands experience stronger electrostatic repulsion than those pointing between the axes [Per Crystal Field Theory].

Step 1: Classification of Energy Levels

  • $e_g$ orbitals: The $d_{x^2-y^2}$ and $d_{z^2}$ orbitals point directly toward the ligands (along the axes). These experience higher repulsion and are destabilized to a higher energy level.
  • $t_{2g}$ orbitals: The $d_{xy}$, $d_{yz}$, and $d_{zx}$ orbitals point between the axes. These experience lower repulsion and are stabilized to a lower energy level.

Step 2: Mathematical Representation of Energy Split

The total energy separation between the two sets is defined as the crystal field splitting energy, denoted as $\Delta_o$.

  • The $e_g$ set is elevated by $+0.6\Delta_o$ above the barycenter.
  • The $t_{2g}$ set is lowered by $-0.4\Delta_o$ below the barycenter.

Step 3: Visual Representation of Orbital Splitting

Increasing Energy d-orbitals (free ion) e_g (d_x^2-y^2, d_z^2) t_{2g} (d_xy, d_yz, d_zx) Δ_o

Step 4: Summary Table of Orbital Energy

Orbital Set Components Energy Adjustment
$e_g$ $d_{x^2-y^2}, d_{z^2}$ $+0.6\Delta_o$
$t_{2g}$ $d_{xy}, d_{yz}, d_{zx}$ $-0.4\Delta_o$

Final Solution: In an octahedral field, the five degenerate d-orbitals split into two sets: a triply degenerate lower-energy $t_{2g}$ set and a doubly degenerate higher-energy $e_g$ set, separated by an energy magnitude of $\Delta_o$.


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