 Jahn-Teller Effect

The Jahn-Teller theorem essentially states that any nonlinear molecule system possessing electronic
degeneracy will be unstable and will undergo distortion to form a system of lower symmetry as well as lower
energy and thus the degeneracy will be removed.
This effect describes the geometrical distortion of molecules and ions that is associated with
electronically degenerate configurations. A configuration is said to be electronically degenerate if more than
one sites are available for the filling of a single electron. The Jahn-Teller effect is generally encountered in
octahedral transition metal complexes. The phenomenon is much more common in hexacoordinated complexes
of bivalent copper. The d9 configuration of Cu2+ ion yields three electrons in the doubly degenerate eg orbitals
set, leading to a doubly degenerate electronic state as well. Such complexes distort along one of the molecular
four-fold axis (always labeled the z-axis), which has the effect of removing the orbital and electronic
degeneracies and lowering the overall energy. The distortion usually occurs via the elongation the metal-ligand
bonds along the z-axis, but sometimes also occurs as a shortening of the same bonds instead. Moreover, the
Jahn-Teller theorem predicts the presence of an unstable geometry only and not the direction of the distortion.
When distortion involving elongation occurs to decrease the electrostatic repulsion between the electron-pair
on the ligand-attached and any extra electrons in metal orbitals with a z-component; and hence lowering the
energy of the metal complex. Inversion center is retained after z-out as well as z-in the distortion. Symmetrical
configurations possess electronic degeneracy while the unsymmetrical ones do not. Various symmetrical and
unsymmetrical configurations are given below.

Table 10. Symmetrical and Unsymmetrical t2g and eg orbitals.

Symmetrical configurations Unsymmetrical configurations

t2g0, t2g3, t2g6 t2g1, t2g2, t2g4, t2g5

eg0, eg4, eg2 (high-spin) eg1, eg3, eg2 (low-spin)

Now, the conditions for different kinds of distortion can be summed up as:

Table 11. Conditions for Jahn-Teller distortion.

Type of distortion Configuration required

No distortion t2g (symmetrical) + eg (symmetrical)

Slight distortion t2g (unsymmetrical)

Strong distortion eg (unsymmetrical)

 Figure 57. The Jahn-Teller distortions for an octahedral complex.

Let the case of the low-spin Co2+ octahedral complex. The corresponding electronic configuration is
t2g6 eg1. Owing to the electronically degenerate state, the Jahn-Teller distortion is expected. Now suppose that
the single electron of eg set is present in dz2 orbital; the ligands approaching from z-axis will feel more repulsion
than the ligands coming from x and y-axis. Therefore, the bonds along z-axis will be weaker in comparison to
the bond along x and y-axis. This results in a tetragonal elongation about z-axis with two longer and four
shorter bonds. This is formally called as z-out distortion. On the other hand, if the single electron of eg set is
present in dx2−y2 orbital; the ligands approaching from x and y-axis will feel more repulsion than the ligands
coming from z-axis. Therefore, the bonds along x and y-axis will be weaker in comparison to the bond along
z-axis. This results in a tetragonally flattened octahedral geometry about z-axis with two shorter and four longer
bonds. This is formally called as z-in distortion.
Consider the following examples
1. [Co(CN)6]4−: It is a low-spin complex with t2g6 eg1 electronic configuration and will undergo strong Jahn-
Teller distortion.
2. [Cr(NH3)6]3+: It is a high-spin complex with t2g3 eg0 electronic configuration which is completely
symmetrical; and therefore, will not show any Jahn-Teller distortion.
3. [FeF6]4−: It is a high-spin complex with t2g4 eg2 electronic configuration and will undergo slight Jahn-Teller
distortion.
 Energetics of Jahn-Teller Distortion
The Jahn-Teller distortion results in a system of lower symmetry and lower energy. This is actually
the opposite of what is expected. Generally, symmetry leads to stability; but the Jahn-Teller effect is actually
an exception to this statement. Therefore, it is necessary to discuss the driving force responsible for this
behavior. The magnitude of Jahn-Teller effect is larger where the electron density associated with the
degenerate set orbitals is more concentrated. Hence, Jahn-Teller effect plays a significant role in determining
the structure of transition metal complexes with active 3d-orbitals. The whole energetics of the Jahn-Teller can
be understood by the case study of d9 and d1 complexes.
1. Cu2+ complexes: The electronic configuration of free Cu2+ ion is d9; and in an octahedral environment, it is
t2g6 eg3. Before we put any conclusive remark on the direction or nature of the distortion, we shall find the
crystal field stabilization energy for z-out as well as for z-in case.
i) Crystal field stabilization energy for z-out distortion:

Figure 58. The splitting pattern and filling of d-orbital set of Cu2+ in octahedral and subsequently in the
tetragonally elongated complex due to Jahn-Teller effect.

CFSE due to distortion = Energy of the distorted complex (E2) − Energy of the complex without distortion (E1)

E1 = 6(−0.4Δo) + 3(+0.6Δo)

E1 = −0.6Δo

E2 = 4(−0.4Δo – δ2/3) + 2(−0.4Δo + 2δ2/3) + 2(+0.6Δo – δ1/2) + 1(+0.6Δo + δ1/2)

E2 = −0.6Δo – δ1/2

CFSE due to distortion = E2 – E1 = –δ1/2

Hence, the crystal field stabilization due to z-out distortion is –δ1/2.

ii) Crystal field stabilization energy for z-in distortion:

Figure 59. The splitting pattern and filling of d-orbital set of Cu2+ in octahedral and subsequently in the
tetragonally compressed complex due to Jahn-Teller effect.

CFSE due to distortion = Energy of the distorted complex (E2) − Energy of the complex without distortion (E1)

E1 = 6(−0.4Δo) + 3(+0.6Δo)

E1 = −0.6Δo

E2 = 4(−0.4Δo – 2δ2/3) + 2(−0.4Δo + δ2/3) + 2(+0.6Δo – δ1/2) + 1(+0.6Δo + δ1/2)

E2 = −0.6Δo – δ1/2

CFSE due to distortion = E2 – E1 = –δ1/2

Hence, the crystal field stabilization due to z-in distortion is –δ1/2.

Hence, the magnitude of crystal field stabilization in z-out case is same as that is present in z-in
complex. This implies that Jahn-Teller effect cannot predict the direction of the distortion. However, it has
been observed that it is the z-out case that dominates in most of the cases. It may depend on the repulsive
forces between the d-electrons and the ligands, so the odd electron will prefer dz2-orbital more than dx2-y2 due
to the lesser number of ligands it will repel with. Moreover, when a z-in distortion occurs, one can also view
it terms of equatorial elongation while z-out will mean the weakening of two axial metal-ligand bonds. In other
words, it is easier to weaken two bonds rather stretching four metal-ligand bonds.
2. Ti3+ complexes: The electronic configuration of free Ti3+ ion is d1; and in an octahedral environment, it is
t2g1 eg0. Before we put any conclusive remark on the direction or nature of the distortion, we shall find the
crystal field stabilization energy for z-out as well as for z-in case.
i) Crystal field stabilization energy for z-out distortion:

Figure 60. The splitting pattern and filling of d-orbital set of Ti3+ in octahedral and subsequently in the
tetragonally elongated complex due to Jahn-Teller effect.

CFSE due to distortion = Energy of the distorted complex (E2) − Energy of the complex without distortion (E1)

E1 = 1(−0.4Δo)

E1 = −0.4Δo

E2 = 1(−0.4Δo – δ2/3)

E2 = −0.4Δo – δ2/3

CFSE due to distortion = E2 – E1 = –δ2/3

Hence, the crystal field stabilization due to z-out distortion is –δ1/3. Moreover, it is worthy to note that this
type of Jahn-Teller distortion is unable to remove the electronic degeneracy completely (the single electron
can still be filled in two degenerate orbitals namely dyz and dzx). Therefore, homoleptic octahedral complexes
of d1-configuration undergoing z-in distortion are quite rare.
ii) Crystal field stabilization energy for z-in distortion:

Figure 61. The splitting pattern and filling of d-orbital set of Ti3+ in octahedral and subsequently in the
tetragonally compressed complex due to the Jahn-Teller effect.

CFSE due to distortion = Energy of the distorted complex (E2) − Energy of the complex without distortion (E1)

E1 = 1(−0.4Δo)

E1 = −0.4Δo

E2 = 1(−0.4Δo – 2δ2/3)

E2 = −0.4Δo – 2δ2/3

CFSE due to distortion = E2 – E1 = –2δ2/3

Hence, the crystal field stabilization due to z-in distortion is –2δ2/3.

Hence, the magnitude of crystal field stabilization in z-out case is half of what is observed in z-in
complex. This implies that Jahn-Teller effect can predict the direction of the distortion. However, it is the d1-
configuration that has been observed to show z-in distortion; otherwise, the z-out case dominates in most of
the cases. It may be explained in terms of the repulsive forces between the d-electrons and the ligands, so the
odd electron will prefer dz2-orbital more than dx2-y2 due to the lesser number of ligands it will repel with.
Nevertheless, Ti3+ octahedral complexes prefer to undergo z-in due to the greater value of crystal field
stabilization energy.
  Effect of Jahn-Teller Distortion on Electronic Spectra
Jahn-Teller distortions affect the UV-visible spectra of many transition metal complexes in a
significant manner and sometimes it is almost impossible to find out the values of the Racah parameter and
crystal splitting energy if we do not take it into account. In UV-visible absorption spectroscopy, distortion
causes the splitting of bands in the spectrum due to a reduction in symmetry (Oh to D4h). The complexes
undergoing Jahn-Teller distortion show an increased number of bands. Consider the following examples:
1. [Cr(H2O)6]2+: The Cr2+ ion in aqueous solutions is pale blue and its UV-visible absorption spectrum consists
of a weak broad band with a maxima 14000 cm−1. In normal conditions, this band is expected to provide the
value of crystal field splitting value directly (from Orgel-diagram of d4-configuration); however, the actual
value of Δo is considerably different. The electronic configuration for high-spin Cr2+ in the octahedral field is
t2g3 eg1; and therefore, this complex is bound to undergo strong Jahn-Teller distortion. The energy level diagram
and main transitions are shown below.

Figure 62. The schematic energy level diagram and prominent transitions in [Cr(H2O)6]2+.

The ground state term for a regular octahedral [Cr(H2O)6]2+ complex would be 5Eg but the ground as
well as excited electronic state will undergo a Jahn-Teller distortion. It is worthy to note that the former state
shows strong while splitting of later one is weak. Hence, the Tanabe-Sugano diagram cannot be used to
describe the energy levels in the complex. The gaussian deconvolution of the overall spectrum has shown that
the transition between the split components of the 5Eg level (5B1g → 5A1g) occurs at around 10000 cm−1 and
contributes to the low-energy tail of the broad band in aqueous solution.