Q.The CFSE for octahedral [CoCl6]4− is 18,000 cm−1. The CFSE for tetrahedral [CoCl4]2− will be
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Crystal Field Splitting: From Intuition to Precision
Imagine you are a negatively charged electron sitting on a metal ion. All around you, the space is perfectly spherical — every direction feels the same. Your energy depends only on how far you are from the nucleus, not on which way you face.
Now imagine that six negative ions (or the negative ends of polar molecules) march in from the x, y, and z axes and stop close to you. Suddenly, the space around you is no longer uniform. If you try to move straight toward one of these approaching ions, you feel a strong repulsion — that path costs extra energy. If you move between the axes (say, along a diagonal), you feel less repulsion because you are farther from the incoming charges.
This is the core intuition: when ligands approach a metal ion, they break the spherical symmetry of the space around the metal. Different directions in space are no longer equivalent. Electrons in orbitals that point directly at the ligands get pushed up in energy; electrons in orbitals that point between the ligands stay lower.
The Precise Statement
Crystal Field Splitting is the splitting of degenerate d orbitals of a transition metal ion into two or more sets of different energies, caused by the electrostatic repulsion between the metal's d electrons and the negative charge (or dipole) of surrounding ligands.
For the most common geometry — octahedral — here is what happens:
- Six ligands sit at the corners of an octahedron, along the +x, −x, +y, −y, +z, −z axes.
- The dx2−y2 and dz2 orbitals point their lobes directly along these axes. These are the eg set. They feel maximum repulsion → higher energy.
- The dxy, dxz, and dyz orbitals point their lobes between the axes (into the octahedral faces). These are the t2g set. They feel less repulsion → lower energy.
The energy gap between these two sets is denoted by Δo (or 10Dq). The t2g set drops by 0.4Δo and the eg set rises by 0.6Δo, keeping the average energy unchanged (the "barycentre" rule).
The labels eg and t2g come from group theory — they describe how the orbitals transform under the symmetry operations of an octahedron. You do not need to memorise the derivation, but the notation is standard in every exam.
Why This Matters
Crystal field splitting explains three things you will see repeatedly:
- Colour — electrons can jump from t2g to eg by absorbing visible light. The gap Δo determines the colour you see.
- Magnetism — if Δo is large, electrons pair up in the lower t2g set (low spin). If Δo is small, electrons spread out (high spin). This changes the number of unpaired electrons. …
Why this formula?
Crystal Field Splitting: Why the Energy Splitting Occurs
Crystal Field Theory (CFT) explains how the d-orbitals of a transition metal ion split in energy when placed in an electrostatic field created by surrounding ligands (anions or polar molecules). The key result is that five degenerate d-orbitals split into two or more sets with different energies. Let's understand why this happens.
1. The Starting Point: Degenerate d-Orbitals
In a free transition metal ion (no ligands), all five d-orbitals have the same energy (degenerate). Their shapes are:
- dxy, dxz, dyz — lobes lie between the x, y, z axes (called t2g set in octahedral symmetry)
- dx2−y2, dz2 — lobes point directly along the x, y, z axes (called eg set)
Key idea: The spatial orientation of each orbital determines how it interacts with approaching ligands.
2. The Octahedral Case: Why eg Orbitals Are Higher in Energy
Imagine six ligands approaching along the +x, –x, +y, –y, +z, –z axes (octahedral geometry).
What happens to dx2−y2 and dz2?
- Their lobes point directly at the ligands.
- The negatively charged ligands repel the electron density in these orbitals.
- This repulsion raises the energy of these orbitals — they become less stable (higher energy).
What happens to dxy, dxz, dyz?
- Their lobes point between the axes (e.g., dxy lobes lie in the xy-plane but at 45° to x and y).
- They avoid the ligands — less repulsion.
- Their energy is lower than the eg set.
The Splitting Pattern
Δoct=E(eg)−E(t2g)
Where:
- E(eg) = energy of dx2−y2 and dz2 (higher)
- E(t2g) = energy of dxy, dxz, dyz (lower)
- Δoct is called the crystal field splitting energy (CFSE)
Why the name? The eg orbitals are "doubly degenerate" (2 orbitals), t2g are "triply degenerate" (3 orbitals). The letters come from group theory symmetry labels.
3. The Energy Conservation Rule
The total energy of all five d-orbitals must remain constant (no energy is created or destroyed). So:
- The center of gravity (average energy) of the split set equals the original degenerate energy.
- For octahedral splitting:
- 2 eg orbitals go up by +0.6Δoct each
- 3 t2g orbitals go down by −0.4Δoct each
Check:
2×(+0.6Δ)+3×(−0.4Δ)=1.2Δ−1.2Δ=0
This conservation of energy is a fundamental constraint — the splitting is not arbitrary.
4. The Tetrahedral Case: Why It's Opposite and Smaller
In a tetrahedral complex, four ligands approach from alternate corners of a cube. The axes are different:
- The dxy, dxz, dyz orbitals now point closer to the ligands (more repulsion).
- The dx2−y2 and dz2 orbitals point away from ligands (less repulsion).
Result:
- e set ( dx2−y2, dz2 ) — lower energy
- t2 set ( dxy, dxz, dyz ) — higher energy
The splitting is inverted compared to octahedral.
Magnitude:
Δtet≈94Δoct
Why smaller?
- Only 4 ligands (vs. 6) → less total repulsion.
- Ligands are not directly along axes → weaker interaction. …
Concept: Crystal Field Splitting — the splitting energy (Δ) depends on geometry and ligand field strength. For the same metal ion and ligand, Δt≈94Δo.
Reasoning:
- Both complexes have Co(II) (d7) with Cl⁻ ligands. In octahedral [CoCl6]4−, CFSE = 18,000 cm−1 is actually the value of Δo (since for high-spin d7, CFSE = 0.8Δo, but here the given number is the splitting itself). …
Using the standard relation Δt=94Δo, the tetrahedral stabilization scales as 94 of the octahedral value: 94×18,000=8,000 cm−1. The answer is (iii).
Setup. In both complexes the metal is Co2+ (d7) with the same weak-field Cl− ligands. The only quantity that changes on going from octahedral to tetrahedral geometry is the size of the crystal-field splitting.
Key relation. For the same metal ion and the same ligands,
Δt=94Δo. …
Method: Crystal Field Splitting Ratio Rule for Tetrahedral vs Octahedral Complexes
Why this method works
In crystal field theory, the crystal field splitting energy (Δt) for a tetrahedral complex is related to that of an octahedral complex (Δo) by a fixed ratio:
Δt=94Δo
This comes from the fact that:
- Tetrahedral complexes have only 4 ligands (vs 6 in octahedral)
- The ligand approach direction is less direct in tetrahedral geometry
- The d-orbital splitting pattern is inverted and smaller in magnitude
Steps to solve
Step 1: Identify the given data
- Complex: [CoCl6]4− (octahedral)
- Δo=18,000 cm−1
- Target: Δt for [CoCl4]2− (tetrahedral)
Step 2: Apply the ratio rule
Δt=94×Δo
Step 3: Substitute and calculate
Δt=94×18,000 …
Common Mistakes Students Make on This CFSE Problem
Mistake 1: Forgetting the Geometry Factor (Δₜ = 4/9 Δₒ)
The error: Students directly use the same CFSE value for tetrahedral as octahedral, or apply a wrong ratio.
Why it’s wrong:
Crystal Field Splitting in tetrahedral complexes is smaller than in octahedral. The relationship is:
Δt=94Δo
Here, Δo=18,000 cm−1, so:
Δt=94×18,000=8,000 cm−1
How to avoid: Always recall: tetrahedral splitting is always 94 of octahedral splitting for the same metal and ligand.
Mistake 2: Ignoring the d-electron Count and CFSE Formula
The error: Students calculate Δt but forget that CFSE depends on how electrons fill the t2 and e orbitals.
Why it’s wrong:
For [CoCl6]4−, Co is in +2 state → d7 configuration.
In octahedral: t2g5eg2 (high spin, weak field ligand Cl⁻).
CFSE = [5×(−0.4)+2×(0.6)]Δo=(−2+1.2)Δo=−0.8Δo
For tetrahedral [CoCl4]2− (also d7, weak field):
Configuration: e4t23
CFSE = [4×(−0.6)+3×(0.4)]Δt=(−2.4+1.2)Δt=−1.2Δt
So CFSE (tet) = −1.2×8,000=−9,600 cm−1 — but the question asks for Δt, not CFSE.
How to avoid: Read carefully — does the question ask for CFSE or Δ? Here it asks for CFSE of tetrahedral, which is not simply 94× octahedral CFSE.
Mistake 3: Confusing Δ with CFSE
The error: Students treat Δ and CFSE as the same quantity.
Why it’s wrong:
Δ is the splitting energy between t2 and e sets.
CFSE is the net energy stabilization after placing electrons, given by:
CFSE=[−0.4×n(t2g)+0.6×n(eg)]Δo(octahedral)
CFSE=[−0.6×n(e)+0.4×n(t2)]Δt(tetrahedral)
How to avoid: Always write the electron configuration and apply the correct CFSE formula — never skip this step.
Mistake 4: Using the Wrong d-Orbital Splitting Pattern
The error: Students apply octahedral orbital labels (t2g,eg) to tetrahedral geometry.
Why it’s wrong:
In tetrahedral, the splitting is inverted:
- Lower energy: e set (dx2−y2,dz2) …
- GSEB Higher Secondary Certificate (HSC) Examination 2026Set ANNUAL1 markMCQQ.The crystal field splitting energy for octahedral (delta o) and tetrahedral (delta t) complexes is related as(a) delta t = 1/2 delta o(b) delta t = 4/9 delta o(c) delta t = 3/9 delta o(d) delta t = 3/2 delta o
›Reveal solutionSolution
By crystal field theory, the tetrahedral crystal field splitting energy is always 4/9 of the octahedral splitting energy for the same metal ion and ligands.
In an octahedral field, 6 ligands point directly at the d-orbitals, producing a relatively large splitting (Δo). In a tetrahedral field, only 4 ligands are present and none point directly at any d-orbital (they approach between the axes), which weakens the splitting considerably. Crystal field theory shows the two splittings are rela …
- GUJCET 2025Set 031 markMCQQ.According to crystal field theory for which of the following coordination entities Δ0 is maximum? (A) [CoCl(NH3)5]2+ (B) [Co(NH3)6]3+ (C) [Co(CN)6]3− (D) [Co(NH3)5(H2O)]3+
›Reveal solutionSolution
[!TLDR]
[Co(CN)6]3− has the maximum Δ0 because CN− is the strongest-field ligand.
Concept
For a given metal and oxidation state, the crystal-field splitting energy Δ0 increases with the field strength of the ligands, ordered by the spectrochemical series: Cl−<H2O<NH3<CN−.
Solution
Cobalt is Co3+ (d6) in every option, so compare ligand fields:
- [CoCl(NH3)5]2+: one weak Cl− plus five NH3 — lowered field.
- [Co(NH3)5(H2O)]3+: one H2O (weaker than NH3) plus five NH3. …
- GUJCET 2023Set 091 markMCQQ.How t2g4eg0 configuration is possible for d4 ion during crystal Field splitting in Octahedral complex? (A) Δ0=P (B) Δ0≤P (C) Δ0<P (D) Δ0>P
›Reveal solutionSolution
Electrons pair in t2g (low spin) only when the splitting exceeds the pairing energy: Δ0>P.
Concept: For a d4 octahedral ion, the fourth electron either enters eg (high spin, t2g3eg1) or pairs in t2g (low spin, t2g4eg0). Pairing is favoured when …
- GSEB Higher Secondary Certificate (HSC) Examination 2022Set ANNUAL1 markMCQQ.For a high-spin complex, which relation is correct (comparing crystal field splitting energy Delta and pairing energy P)?(a) Delta < P(b) Delta = P(c) Delta > P(d) Delta0 >= P
›Reveal solutionSolution
Whether electrons pair up in the lower t2g set or spread out with parallel spins into eg depends on comparing the crystal field splitting energy (Delta) with the pairing energy (P).
If Delta (the energy gap created by the ligand field) is SMALLER than the pairing energy P, it costs less energy for electrons to occupy the higher eg orbitals singly (Hund's rule) than to pair up in t2g - this gives the maximum number of unpaired electro …
- GUJCET 2020Set 071 markMCQQ.Which of the following complex will absorb maximum wavelength of light? (A) [Co(NH3)6]3+ (B) [Co(NH3)5(H2O)]3+ (C) [CoCl(NH3)5]2+ (D) [Co(CN)6]3−
›Reveal solutionSolution
Longest λ ⇔ smallest crystal-field split Δo; [CoCl(NH3)5]2+ has the weakest-field set.
Concept — spectrochemical series. λmax∝1/Δo. Field strength: CN−>NH3>H2O>Cl−. Replacing an NH₃ with the weak-field Cl⁻ gives the lowest Δo of the set, hence absorption …
- GUJCET 2019Set 131 markMCQQ.What is the correct order for energy of d orbitals splitting in Tetra Chlorido Nickelate (II) complex ion? (A) dx2−y2>dz2>dxy≅dyz≅dz2 (B) dxy≅dyz≅dzx>dx2−y2≅dz2 (C) dxy≅dyz≅dxy≅dx2−y2≅dz2 (D) dxy≅dyz≅dxy<dx2−y2≅dz2
›Reveal solutionSolution
Tetrachloridonickelate(II) is tetrahedral, so t2(dxy,dyz,dzx) are HIGHER in energy than e(dx2−y2,dz2).
Concept: [NiCl4]2− has Cl− (weak field) around Ni2+; it is tetrahedral. In a tetrahedral field the d-orbital splitting is the inverse of octahedral: the three t2 orbitals (dxy,dyz,dzx) point closer to the ligand approach directions and are raised, while the two e orbitals (dx2−y2,dz2) are lowered.
Thus the correct energy order is: …
- GSEB Higher Secondary Certificate (HSC) Examination 2019Set ANNUAL1 markMCQQ.For which complex from following value of delta-o (crystal field splitting energy) will be lowest?(a) [Co(NH3)6]3+(b) [Co(CN)6]3-(c) [Co(H2O)6]3+(d) [Co(C2O4)3]3-
›Reveal solutionSolution
Crystal field splitting energy (delta-o) depends on the field strength of the coordinated ligand, ranked by the spectrochemical series.
The spectrochemical series (increasing field strength, hence increasing delta-o) relevant here is approximately:
C2O4^2- (oxalate) < H2O < NH3 < CN- …
- GUJCET 2015Set C1 markMCQQ.Which of the following spectrochemical series is true? (A) SCN−<F−<NH3<en<CO (B) SCN−<NH3<F−<en<CO (C) SCN−<F−<en<NH3<CO (D) SCN−<F−<en<CO<NH3
›Reveal solutionSolution
[!TLDR] Correct increasing field strength: SCN− < F− < NH3 < en < CO.
Concept
The spectrochemical series ranks ligands by the crystal-field splitting they produce. A commonly used ordering (weak to strong field) is:
I−<Br−<SCN−<Cl−<F−<OH−<ox<H2O<NH3<en<CN−<CO.
Solution
Place the given ligands on this scale:
- SCN− (S-bonded, thiocyanate) — weak field, lowest here.
- F− — stronger than SCN−.
- NH3 — stronger than F−. …
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