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2007 7 PDF

The ligand-field spectrum of [Ni(H2O)6]2+ shows three bands. [1] In an octahedral field, the d-orbitals of Ni2+ split into lower energy t2g and higher energy eg orbitals. [2] Transitions from the ground (t2g)6(eg)2 configuration can lead to the (t2g)5(eg)3 and (t2g)4(eg)4 excited configurations, giving two possible transitions. [3] However, interelectron repulsion between electrons in the (t2g)5(eg)3 configuration splits it into two levels, producing the three observed bands.

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50 views

2007 7 PDF

The ligand-field spectrum of [Ni(H2O)6]2+ shows three bands. [1] In an octahedral field, the d-orbitals of Ni2+ split into lower energy t2g and higher energy eg orbitals. [2] Transitions from the ground (t2g)6(eg)2 configuration can lead to the (t2g)5(eg)3 and (t2g)4(eg)4 excited configurations, giving two possible transitions. [3] However, interelectron repulsion between electrons in the (t2g)5(eg)3 configuration splits it into two levels, producing the three observed bands.

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muhdhaziq
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Bridgeman 2007 Page 7

The picture below shows the ligand-field spectrum of the [Ni(H2O)6] ion. 2+

8 (i) Explain, with the aid of diagrams, why there are three bands in the spectrum.

As nickel is in Group 10, Ni2+ has (Group number oxidation number) = (10 2) = 8 d-
electrons: d8.

Without considering the effects of interelectron repulsion, it appears that there are just
two possible transitions. In an octahedral field, the d-orbitals split up into a set of two low
energy orbitals (dz2 and dx2-y2 labelled eg), which point straight at the ligands, and a set of
three low energy orbitals (dxy, dxz and dyz labelled as t2g), which point between the ligands.
The gap between them equal to oct.

The ground configuration has a (t2g)6(eg)2 arrangement and the two possible excited
configurations have (t2g)6(eg)2 and (t2g)6(eg)2 arrangements, with energies oct and 2oct,
respectively:

eg eg eg

t 2g t 2g t 2g

ground configuration: 1st excited conf iguration: 2nd excited conf iguration:
t 2g6eg2 t 2g5eg3 t 2g4eg4

However, there are six possible arrangements for the electrons in the (t2g)5(eg)3
configuration and these differ due to the extent of repulsion between the d-electrons
themselves. For example, arrangements with one electron in dz2 and one in dxz have less
crowded electron density and lower repulsion than arrangements with one in dz2 and one
in dxz:
z z

y y

x x

(dz2)2(dxz)2 (dz2)1(dxz)1
Bridgeman 2007 Page 7
5 3
The six arrangements making up the (t2g) (eg) configuration can be grouped together
into two sets according to high or low interelectron repulsion.

Because of the effect of repulsion between the d-electrons, the configuration (t2g)5(eg)3 thus
leads to two possible energy levels. There are therefore 3 possible transitions from the
ground (e)2 configuration:

(i) (t2g)6(eg)2 (t2g)5(eg)3 (low repulsion set)


(ii) (t2g)6(eg)2 (t2g)5(eg)3 (high repulsion set)
(i) (t2g)6(eg)2 (t2g)4(eg)2

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