Crystal eld theory

Crystal Field Theory (CFT) is a model that describes

the breaking of degeneracies of electron orbital states,
usually d or f orbitals, due to a static electric eld produced by a surrounding charge distribution (anion neighbors). This theory has been used to describe various spectroscopies of transition metal coordination complexes, in
particular optical spectra (colors). CFT successfully accounts for some magnetic properties, colours, hydration
enthalpies, and spinel structures of transition metal complexes, but it does not attempt to describe bonding. CFT
was developed by physicists Hans Bethe and John Hasbrouck van Vleck[1] in the 1930s. CFT was subsequently
combined with molecular orbital theory to form the more
realistic and complex ligand eld theory (LFT), which
delivers insight into the process of chemical bonding in
transition metal complexes.

hedral symmetry the d-orbitals split into two sets with an

energy dierence, (the crystal-eld splitting parameter) where the dxy, dxz and dyz orbitals will be lower in
energy than the dz2 and dx2 -y2 , which will have higher
energy, because the former group is farther from the ligands than the latter and therefore experience less repulsion. The three lower-energy orbitals are collectively referred to as t , and the two higher-energy orbitals as e .
(These labels are based on the theory of molecular symmetry). Typical orbital energy diagrams are given below
in the section High-spin and low-spin.

Tetrahedral complexes are the second most common

type; here four ligands form a tetrahedron around the
metal ion. In a tetrahedral crystal eld splitting the dorbitals again split into two groups, with an energy dierence of where the lower energy orbitals will be dz2
and dx2 -y2 , and the higher energy orbitals will be dxy,
dxz and dyz - opposite to the octahedral case. Further1 Overview of crystal eld theory more, since the ligand electrons in tetrahedral symmetry
are not oriented directly towards the d-orbitals, the enanalysis
ergy splitting will be lower than in the octahedral case.
Square planar and other complex geometries can also be
According to CFT, the interaction between a transition
described by CFT.
metal and ligands arises from the attraction between the
positively charged metal cation and negative charge on the The size of the gap between the two or more sets
non-bonding electrons of the ligand. The theory is devel- of orbitals depends on several factors, including the ligoped by considering energy changes of the ve degenerate ands and geometry of the complex. Some ligands always
d-orbitals upon being surrounded by an array of point produce a small value of , while others always give a
charges consisting of the ligands. As a ligand approaches large splitting. The reasons behind this can be explained
the metal ion, the electrons from the ligand will be closer by ligand eld theory. The spectrochemical series is an
to some of the d-orbitals and farther away from others empirically-derived list of ligands ordered by the size of
causing a loss of degeneracy. The electrons in the d- the splitting that they produce (small to large ; see
orbitals and those in the ligand repel each other due to re- also this table):
pulsion between like charges. Thus the d-electrons closer I < Br < S2 < SCN < Cl < NO < N < F < OH
3
3
to the ligands will have a higher energy than those further < C O 2 < H O < NCS < CH CN < py < NH < en <
2 4
2
3
3
away which results in the d-orbitals splitting in energy. 2,2'-bipyridine < phen < NO < PPh < CN < CO
2
3
This splitting is aected by the following factors:
It is useful to note that the ligands producing the most
splitting are those that can engage in metal to ligand back the nature of the metal ion.
bonding.
the metals oxidation state. A higher oxidation state
The oxidation state of the metal also contributes to the
leads to a larger splitting.
size of between the high and low energy levels. As the
the arrangement of the ligands around the metal ion. oxidation state increases for a given metal, the magnitude
of increases. A V3+ complex will have a larger than a
the nature of the ligands surrounding the metal ion.
V2+ complex for a given set of ligands, as the dierence in
The stronger the eect of the ligands then the greater
charge density allows the ligands to be closer to a V3+ ion
the dierence between the high and low energy d
than to a V2+ ion. The smaller distance between the ligand
groups.
and the metal ion results in a larger , because the ligand
and metal electrons are closer together and therefore repel
The most common type of complex is octahedral; here six
more.
ligands form an octahedron around the metal ion. In octa1

1.1

High-spin and low-spin

CRYSTAL FIELD STABILIZATION ENERGY

cost of placing an electron in an eg, , high spin splitting

occurs.

Main article: Spin states (d electrons)

The crystal eld splitting energy for tetrahedral metal
See also: Magnetochemistry
complexes (four ligands) is referred to as , and is
Ligands which cause a large splitting of the d-orbitals roughly equal to 4/9 (for the same metal and same
ligands). Therefore, the energy required to pair two electrons is typically higher than the energy required for placing electrons in the higher energy orbitals. Thus, tetrahedral complexes are usually high-spin.

Low Spin [Fe(NO2 )6 ]3 crystal eld diagram

are referred to as strong-eld ligands, such as CN and

CO from the spectrochemical series. In complexes with
these ligands, it is unfavourable to put electrons into the
high energy orbitals. Therefore, the lower energy orbitals
are completely lled before population of the upper sets
starts according to the Aufbau principle. Complexes such
as this are called low spin. For example, NO2 is a
strong-eld ligand and produces a large . The octahedral
ion [Fe(NO2 )6 ]3 , which has 5 d-electrons, would have
the octahedral splitting diagram shown at right with all
ve electrons in the tg level.

The use of these splitting diagrams can aid in the prediction of the magnetic properties of coordination compounds. A compound that has unpaired electrons in its
splitting diagram will be paramagnetic and will be attracted by magnetic elds, while a compound that lacks
unpaired electrons in its splitting diagram will be diamagnetic and will be weakly repelled by a magnetic eld.

2 Crystal eld stabilization energy

The crystal eld stabilization energy (CFSE) is the stability that results from placing a transition metal ion in the
crystal eld generated by a set of ligands. It arises due to
the fact that when the d-orbitals are split in a ligand eld
(as described above), some of them become lower in energy than before with respect to a spherical eld known as
the barycenter in which all ve d-orbitals are degenerate.
For example, in an octahedral case, the t2g set becomes
lower in energy than the orbitals in the barycenter. As a
result of this, if there are any electrons occupying these
orbitals, the metal ion is more stable in the ligand eld relative to the barycenter by an amount known as the CFSE.
Conversely, the eg orbitals (in the octahedral case) are
higher in energy than in the barycenter, so putting electrons in these reduces the amount of CFSE.

High Spin [FeBr6 ]3 crystal eld diagram

Conversely, ligands (like I and Br ) which cause a small

splitting of the d-orbitals are referred to as weak-eld
ligands. In this case, it is easier to put electrons into the
higher energy set of orbitals than it is to put two into
the same low-energy orbital, because two electrons in the
same orbital repel each other. So, one electron is put into
each of the ve d-orbitals before any pairing occurs in
accord with Hunds rule and high spin complexes are
formed. For example, Br is a weak-eld ligand and produces a small . So, the ion [FeBr6 ]3 , again with ve
d-electrons, would have an octahedral splitting diagram
where all ve orbitals are singly occupied.

Octahedral crystal eld stabilization energy

If the splitting of the d-orbitals in an octahedral eld is

, the three t2g orbitals are stabilized relative to the
barycenter by 2 /5 , and the eg orbitals are destabilized
by 3 /5 . As examples, consider the two d5 congurations shown further up the page. The low-spin (top)
example has ve electrons in the t2g orbitals, so the total CFSE is 5 x 2 /5 = 2 . In the high-spin (lower)
example, the CFSE is (3 x 2 /5 ) - (2 x 3 /5 ) = 0
- in this case, the stabilization generated by the electrons
in the lower orbitals is canceled out by the destabilizing
eect of the electrons in the upper orbitals.

In order for low spin splitting to occur, the energy cost

of placing an electron into an already singly occupied orbital must be less than the cost of placing the additional
electron into an eg orbital at an energy cost of . As noted
above, eg refers to the dz2 and dx2 -y2 which are higher in
energy than the t in octahedral complexes. If the energy Crystal Field stabilization is applicable to transition-metal
required to pair two electrons is greater than the energy complexes of all geometries. Indeed, the reason that

3
many d8 complexes are square-planar is the very large will appear if it only has one absorption in the visible
amount of crystal eld stabilization that this geometry spectrum. For example, if the compound absorbs red
produces with this number of electrons.
light, it will appear green.

Explaining the colors of transition metal complexes

The bright colors exhibited by many coordination compounds can be explained by Crystal Field Theory. If the
d-orbitals of such a complex have been split into two sets
as described above, when the molecule absorbs a photon
of visible light one or more electrons may momentarily
jump from the lower energy d-orbitals to the higher energy ones to transiently create an excited state atom. The
dierence in energy between the atom in the ground state
and in the excited state is equal to the energy of the absorbed photon, and related inversely to the wavelength of
the light. Because only certain wavelengths () of light are
absorbed - those matching exactly the energy dierence
- the compounds appears the appropriate complementary
color.
As explained above, because dierent ligands generate
crystal elds of dierent strengths, dierent colors can
be seen. For a given metal ion, weaker eld ligands create a complex with a smaller , which will absorb light of
longer and thus lower frequency . Conversely, stronger
eld ligands create a larger , absorb light of shorter ,
and thus higher . It is, though, rarely the case that the
energy of the photon absorbed corresponds exactly to the
size of the gap ; there are other things (such as electronelectron repulsion and Jahn-Teller eects) that also affect the energy dierence between the ground and excited
states.

absorbed versus color observed

400 nm Violet absorbed, Green-yellow observed ( 560
nm)
450 nm Blue absorbed, Yellow observed ( 600 nm)
490 nm Blue-green absorbed, Red observed ( 620 nm)
570 nm Yellow-green absorbed, Violet observed ( 410
nm)
580 nm Yellow absorbed, Dark blue observed ( 430 nm)
600 nm Orange absorbed, Blue observed ( 450 nm)
650 nm Red absorbed, Green observed ( 520 nm)

4 Crystal eld splitting diagrams

5 See also
Schottky anomaly low temperature spike in heat
capacity seen in materials containing high-spin magnetic impurities, often due to crystal eld splitting.
Ligand eld theory
Molecular orbital theory

6 Gallery
Octahedral
Pentagonal bipyramidal
Square antiprismatic

3.1

Which colors are exhibited?

Square planar
Square pyramidal

Red
Orange

Rose

Magenta

Tetrahedral
Yellow

Chartreuse
Green

Violet

Green

Blue

Azure

Cyan

Spring
Green

Color wheel

This color wheel demonstrates which color a compound

Trigonal bipyramidal

7 References
[1] Van Vleck, J. (1932).
Theory of the Variations in Paramagnetic Anisotropy Among Different Salts of the Iron Group.
Physical ReBibcode:1932PhRv...41..208V.
view 41:
208.
doi:10.1103/PhysRev.41.208.

Zumdahl, Steven S (2005). Chemical Principles (5th

ed.). Houghton Miin Company. pp. 550551,
957964. ISBN 0-669-39321-5.

8
Silberberg, Martin S (2006). Chemistry: The Molecular Nature of Matter and Change (4th ed.). New
York: McGraw Hill Company. pp. 10281034.
ISBN 0-8151-8505-7.
Shriver, D. F.; Atkins, P. W. (2001). Inorganic
Chemistry (4th ed.). Oxford University Press. pp.
227236. ISBN 0-8412-3849-9.
Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic
Chemistry (2nd ed.). Prentice Hall. ISBN 9780130399137.
Miessler, G. L.; Tarr, D. A. (2003). Inorganic
Chemistry (3rd ed.). Pearson Prentice Hall. ISBN
0-13-035471-6.

External links
Crystal-eld Theory, Tight-binding Method, and
Jahn-Teller Eect in E. Pavarini, E. Koch, F. Anders, and M. Jarrell (eds.): Correlated Electrons:
From Models to Materials, Jlich 2012, ISBN 9783-89336-796-2
Crystal eld theory
Citizendium.org

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article)

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