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Crystal Field Theory

Introduction to Crystal Field Theory

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One of the most striking characteristics of transition-metal complexes is the

wide range of colors they exhibit (Figure 23.4) and Figure 23.5). In this section, we
describe crystal field theory (CFT), a bonding model that explains many important
properties of transition-metal complexes, including their colors, magnetism,
structures, stability, and reactivity. The central assumption of CFT is that metal
ligand interactions are purely electrostatic in nature. Even though this assumption
is clearly not valid for many complexes, such as those that contain neutral ligands
like CO, CFT enables chemists to explain many of the properties of transitionmetal complexes with a reasonable degree of accuracy. The Learning Objective of
this Module is to understand how crystal field theory explains the electronic
structures and colors of metal complexes.
d - ORBITAL SPLITTINGS
CFT focuses on the interaction of the five (n 1)d orbitals with ligands
arranged in a regular array around a transition-metal ion. We will focus on the
application of CFT to octahedral complexes, which are by far the most common
and the easiest to visualize. Other common structures, such as square planar
complexes, can be treated as a distortion of the octahedral model. According to
CFT, an octahedral metal complex forms because of the electrostatic interaction
of a positively charged metal ion with six negatively charged ligands or with the
negative ends of dipoles associated with the six ligands. In addition, the ligands
interact with one other electrostatically. As you learned in our discussion of the
valence-shell

electron-pair

repulsion

(VSEPR)

model,

the

lowest-energy

arrangement of six identical negative charges is an octahedron, which minimizes

repulsive interactions between the ligands.
We begin by considering how the energies of the d orbitals of a transitionmetal ion are affected by an octahedral arrangement of six negative charges.
Recall that the five d orbitals are initially degenerate (have the same energy). If
we distribute six negative charges uniformly over the surface of a sphere, the d
orbitals remain degenerate, but their energy will be higher due to repulsive
electrostatic interactions between the spherical shell of negative charge and
electrons in the d orbitals (part (a) in Figure 23.10). Placing the six negative
charges at the vertices of an octahedron does not change the average energy of
the d orbitals, but it does remove their degeneracy: the five d orbitals split into
two groups whose energies depend on their orientations. As shown in part (b) in
Figure 23.10, the dz2 and dx2y2 orbitals point directly at the six negative charges
located on the x, y, and z axes. Consequently, the energy of an electron in these

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two orbitals (collectively labeled the e g orbitals) will be greater than it will be for a
spherical distribution of negative charge because of increased electrostatic
repulsions. In contrast, the other three d orbitals (d xy, dxz, and dyz, collectively
called the t2g orbitals) are all oriented at a 45 angle to the coordinate axes, so
they point between the six negative charges. The energy of an electron in any of
these three orbitals is lower than the energy for a spherical distribution of
negative charge.

Figure 23.10 An Octahedral Arrangement of Six Negative Charges around a

Metal Ion Causes the Five d Orbitals to Split into Two Sets with Different Energies.
(a) Distributing a charge of 6 uniformly over a spherical surface surrounding a
metal ion causes the energy of all five d orbitals to increase due to electrostatic
repulsions, but the five d orbitals remain degenerate. Placing a charge of 1 at
each vertex of an octahedron causes the d orbitals to split into two groups with
different energies: the dx2y2 and dz2 orbitals increase in energy, while the, d xy,
dxz, and dyz orbitals decrease in energy. The average energy of the five d orbitals
is the same as for a spherical distribution of a 6 charge, however. Attractive
electrostatic interactions between the negatively charged ligands and the
positively charged metal ion (far right) cause all five d orbitals to decrease in
energy but does not affect the splittings of the orbitals. (b) The two e g orbitals
(left) point directly at the six negatively charged ligands, which increases their
energy compared with a spherical distribution of negative charge. In contrast, the

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three t2gorbitals (right) point between the negatively charged ligands, which
decreases their energy compared with a spherical distribution of charge.
The difference in energy between the two sets of d orbitals is called
the crystal field splitting energy (o), where the subscript o stands for octahedral.
As we shall see, the magnitude of the splitting depends on the charge on the
metal ion, the position of the metal in the periodic table, and the nature of the
ligands. (Crystal field splitting energy also applies to tetrahedral complexes: t.) It
is important to note that the splitting of the d orbitals in a crystal field does not
change the total energy of the five d orbitals: the two e g orbitals increase in
energy by 0.6o, whereas the three t2g orbitals decrease in energy by 0.4 o. Thus
the total change in energy is 2(0.6o) + 3(0.4o) = 0.
Note the Pattern
Crystal field splitting does not change the total energy of the d orbitals.
Thus far, we have considered only the effect of repulsive electrostatic
interactions between electrons in the d orbitals and the six negatively charged
ligands, which increases the total energy of the system and splits the d orbitals.
Interactions between the positively charged metal ion and the ligands results in a
net stabilization of the system, which decreases the energy of all five d orbitals
without affecting their splitting (as shown at the far right in part (a) in Figure
23.10).
ELECTRONIC STRUCTURES OF METAL COMPLEXES
We can use the d-orbital energy-level diagram in Figure 23.10 to predict
electronic structures and some of the properties of transition-metal complexes.
We start with the Ti3+ ion, which contains a single d electron, and proceed across
the first row of the transition metals by adding a single electron at a time. We
place additional electrons in the lowest-energy orbital available, while keeping
their spins parallel as required by Hunds rule. As shown in Figure 23.11, for d1
d3 systemssuch as [Ti(H2O)6]3+, [V(H2O)6]3+, and [Cr(H2O)6]3+, respectivelythe
electrons successively occupy the three degenerate t 2g orbitals with their spins
parallel, giving one, two, and three unpaired electrons, respectively. We can
summarize this for the complex [Cr(H2O)6]3+, for example, by saying that the
chromium ion has a d3 electron configuration or, more succinctly, Cr3+ is a d3 ion.

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Figure 23.11 The Possible Electron Configurations for Octahedral d n TransitionMetal Complexes (n = 110). Two different configurations are possible for
octahedral complexes of metals with d 4, d5, d6, and d7 configurations; the
magnitude of o determines which configuration is observed.
When we reach the d4 configuration, there are two possible choices for the
fourth electron: it can occupy either one of the empty e g orbitals or one of the
singly occupied t2g orbitals. Recall that placing an electron in an already occupied
orbital results in electrostatic repulsions that increase the energy of the system;
this increase in energy is called the spin-pairing energy (P). If o is less than P,
then the lowest-energy arrangement has the fourth electron in one of the empty
eg orbitals. Because this arrangement results in four unpaired electrons, it is called
a high-spin configuration, and a complex with this electron configuration, such as
the [Cr(H2O)6]2+ ion, is called a high-spin complex. Conversely, if o is greater than
P, then the lowest-energy arrangement has the fourth electron in one of the
occupied t2g orbitals. Because this arrangement results in only two unpaired
electrons, it is called a low-spin configuration, and a complex with this electron
configuration, such as the [Mn(CN)6]3 ion, is called a low-spin complex. Similarly,
metal ions with the d5, d6, or d7 electron configurations can be either high spin or
low spin, depending on the magnitude of o.
In contrast, only one arrangement of d electrons is possible for metal ions
with d8d10 electron configurations. For example, the [Ni(H2O)6]2+ion is d8 with two
unpaired electrons, the [Cu(H2O)6]2+ ion is d9 with one unpaired electron, and the
[Zn(H2O)6]2+ ion is d10 with no unpaired electrons.
Note the Pattern
If o is less than the spin-pairing energy, a high-spin configuration results.
Conversely, if o is greater, a low-spin configuration forms.
FACTORS THAT AFFECT THE MAGNITUDE OF o
The magnitude of o dictates whether a complex with four, five, six, or seven
d electrons is high spin or low spin, which affects its magnetic properties,
structure, and reactivity. Large values of o (i.e., o > P) yield a low-spin complex,
whereas small values of o (i.e., o < P) produce a high-spin complex. As we
noted, the magnitude of o depends on three factors: the charge on the metal ion,

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the principal quantum number of the metal (and thus its location in the periodic
table), and the nature of the ligand. Values of o for some representative
transition-metal complexes are given in Table 23.10.
Table 23.10 Crystal Field Splitting Energies for Some Octahedral (o)*
and Tetrahedral (t) Transition-Metal Complexes
Octahedral

o (cm1 Octahedral

o (cm1 Tetrahedral

t (cm1

Complexes

Complexes

Complexes

*Energies obtained by spectroscopic measurements are often given in units of

wave numbers (cm1); the wave number is the reciprocal of the wavelength of
the corresponding electromagnetic radiation expressed in centimeters: 1 cm 1 =
11.96 J/mol.
[Ti(H2O)6]3+

20,300

[Fe(CN)6]4

2+

12,600

[Fe(CN)6]

[V(H2O)6]3+

18,900

[CrCl6]3

[V(H2O)6]

32,800
35,000

[CoCl4]

3300

[CoF6]3

13,000

[CoBr4]2

2900

13,000

[Co(H2O)6]2+

9300

[CoI4]2

2700

13,900

3+

27,000

3+

22,900

[Cr(H2O)6]
[Cr(H2O)6]

3+

17,400

[Co(NH3)6]

[Cr(NH3)6]3+

21,500

[Co(CN)6]3

34,800

[Cr(CN)6]3

26,600

[Ni(H2O)6]2+

8500

34,150

2+

[MnCl6]

[Co(H2O)6]

[Ni(NH3)6]
3

10,800

7500

[RhCl6]

[Mn(H2O)6]2+

8500

[Rh(H2O)6]3+

27,000

[MnCl6]3

20,000

[Rh(NH3)6]3+

34,000

[Mn(H2O)6]
[Fe(H2O)6]

3+

2+

9010
2

2+

Cr(CO)6

VCl4

21,000
10,400

[Rh(CN)6]
[IrCl6]

20,400

45,500
25,000

[Fe(H2O)6]3+
14,300
[Ir(NH3)6]3+
41,000
Source of data: Duward F. Shriver, Peter W. Atkins, and Cooper H. Langford,
Inorganic Chemistry, 2nd ed. (New York: W. H. Freeman and Company, 1994).
1. CHARGE ON THE METAL ION
Increasing the charge on a metal ion has two effects: the radius of the
metal ion decreases, and negatively charged ligands are more strongly
attracted to it. Both factors decrease the metalligand distance, which in turn
causes the negatively charged ligands to interact more strongly with the d
orbitals. Consequently, the magnitude of o increases as the charge on the
metal ion increases. Typically, o for a tripositive ion is about 50% greater
than for the dipositive ion of the same metal; for example, for [V(H 2O)6]2+,
o = 11,800 cm1; for [V(H2O)6]3+, o = 17,850 cm1.
2. PRINCIPAL QUANTUM NUMBER OF THE METAL

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For a series of complexes of metals from the same group in the periodic
table with the same charge and the same ligands, the magnitude of
o increases with increasing principal quantum number: o (3d) < o (4d) <
o (5d). The data for hexaammine complexes of the trivalent group 9 metals
illustrate this point:
[Co(NH3)6]3+
o =
3+
[Rh(NH3)6]
o =
[Ir(NH3)6]3+
o =
The increase in o

22,900 cm1
34,100 cm1
40,000 cm1
with increasing principal quantum number is due to

the larger radius of valence orbitals down a column. In addition, repulsive

ligandligand interactions are most important for smaller metal ions.
Relatively speaking, this results in shorter ML distances and stronger d
orbitalligand interactions.
3. THE NATURE OF THE LIGANDS
Experimentally, it is found that the o observed for a series of complexes
of the same metal ion depends strongly on the nature of the ligands. For a
series of chemically similar ligands, the magnitude of o decreases as the
size of the donor atom increases. For example, ovalues for halide complexes
generally decrease in the order F > Cl > Br > I because smaller, more
localized charges, such as we see for F , interact more strongly with the d
orbitals of the metal ion. In addition, a small neutral ligand with a highly
localized lone pair, such as NH3, results in significantly larger o values than
might be expected. Because the lone pair points directly at the metal ion, the
electron density along the ML axis is greater than for a spherical anion such
as F. The experimentally observed order of the crystal field splitting energies
produced by different ligands is called the spectrochemical series, shown
here in order of decreasing o:
COCN>
NO2>en>NH3>SCN>H2O>oxalate2

strong-field ligands
intermediate-field

ligands
>OH>F>acetate>Cl>Br>I
weak-field ligands
The values of o listed in Table 23.10 (" illustrate the effects of the
charge on the metal ion, the principal quantum number of the metal, and the
nature of the ligand.
Note the Pattern
The largest os are found in complexes of metal ions from the third row of the
transition metals with charges of at least +3 and ligands with localized lone
pairs of electrons.
COLORS OF TRANSITION-METAL COMPLEXES
The striking colors exhibited by transition-metal complexes are caused by
excitation of an electron from a lower-energy d orbital to a higher-energy d orbital,

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which is called a dd transition (Figure 23.12 "A "). For a photon to effect such a
transition, its energy must be equal to the difference in energy between the two d
orbitals, which depends on the magnitude of o.

Figure 23.12 A dd Transition. In a dd transition, an electron in one of the

t2g orbitals of an octahedral complex such as the [Cr(H 2O)6]3+ ion absorbs a photon
of light with energy equal to o, which causes the electron to move to an empty or
singly occupied eg orbital.
Recall that the color we observe when we look at an object or a compound is
due to light that is transmitted or reflected, not light that is absorbed, and that
reflected or transmitted light is complementary in color to the light that is
absorbed. Thus a green compound absorbs light in the red portion of the visible
spectrum and vice versa, as indicated by the color wheel. Because the energy of a
photon of light is inversely proportional to its wavelength, the color of a complex
depends on the magnitude of o, which depends on the structure of the complex.
For example, the complex [Cr(NH3)6]3+ has strong-field ligands and a relatively
large o. Consequently, it absorbs relatively high-energy photons, corresponding
to blue-violet light, which gives it a yellow color. A related complex with weak-field
ligands, the [Cr(H2O)6]3+ ion, absorbs lower-energy photons corresponding to the
yellow-green portion of the visible spectrum, giving it a deep violet color.
We can now understand why emeralds and rubies have such different colors,
even though both contain Cr3+ in an octahedral environment provided by six oxide
ions. Although the chemical identity of the six ligands is the same in both cases,
the CrO distances are different because the compositions of the host lattices are
different (Al2O3 in rubies and Be3Al2Si6O18 in emeralds). In ruby, the CrO distances
are relatively short because of the constraints of the host lattice, which increases
the d orbitalligand interactions and makes o relatively large. Consequently,
rubies absorb green light and the transmitted or reflected light is red, which gives
the gem its characteristic color. In emerald, the CrO distances are longer due to
relatively large [Si6O18]12 silicate rings; this results in decreased d orbitalligand

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interactions and a smaller o. Consequently, emeralds absorb light of a longer
wavelength (red), which gives the gem its characteristic green color. It is clear
that the environment of the transition-metal ion, which is determined by the host
lattice, dramatically affects the spectroscopic properties of a metal ion.

Gem-quality crystals of ruby and emerald. The colors of both minerals are
due to the presence of small amounts of Cr3+ impurities in octahedral sites in an
otherwise colorless metal oxide lattice.
CRYSTAL FIELD STABILIZATION ENERGIES
Recall that stable molecules contain more electrons in the lower-energy
(bonding) molecular orbitals in a molecular orbital diagram than in the higherenergy (antibonding) molecular orbitals. If the lower-energy set of d orbitals (the
t2g orbitals) is selectively populated by electrons, then the stability of the complex
increases. For example, the single d electron in a d 1 complex such as
[Ti(H2O)6]3+ is located in one of the t2gorbitals. Consequently, this complex will be
more stable than expected on purely electrostatic grounds by 0.4 o. The
additional stabilization of a metal complex by selective population of the lowerenergy d orbitals is called its crystal field stabilization energy (CFSE). The CFSE of
a complex can be calculated by multiplying the number of electrons in t 2g orbitals
by the energy of those orbitals (0.4 o), multiplying the number of electrons in
eg orbitals by the energy of those orbitals (+0.6o), and summing the two. Table
23.11 gives CFSE values for octahedral complexes with different d electron
configurations. The CFSE is highest for low-spin d 6 complexes, which accounts in
part for the extraordinarily large number of Co(III) complexes known. The other
low-spin configurations also have high CFSEs, as does the d3configuration.
Table 23.11 CFSEs for Octahedral Complexes with Different Electron
Configurations (in Units of o)
High Spin

CFSE (o)

Low Spin

CFSE (o)

0.4

0.8

1.2

0.6

1.6

0.0

2.0

0.4

2.4

0.8

1.8

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High Spin

CFSE (o)

1.2

0.6

10

0.0

Low Spin

CFSE (o)

CFSEs are important for two reasons. First, the existence of CFSE nicely
accounts for the difference between experimentally measured values for bond
energies in metal complexes and values calculated based solely on electrostatic
interactions. Second, CFSEs represent relatively large amounts of energy (up to
several

hundred

kilojoules

per

mole),

which

has

important

chemical

consequences.
Note the Pattern
Octahedral d3 and d8 complexes and low-spin d 6, d5, d7, and d4 complexes exhibit
large CFSEs.

EXAMPLE 7
For each complex, predict its structure, whether it is high spin or low spin, and
the number of unpaired electrons present.
a.
[CoF6]3
b.
[Rh(CO)2Cl2]
Given: complexes
Asked for: structure, high spin versus low spin, and the number of unpaired
electrons
Strategy:
a.
From the number of ligands, determine the coordination number of the
b.

compound.
Classify the ligands as either strong field or weak field and determine the

electron configuration of the metal ion.

c.
Predict the relative magnitude of o and decide whether the compound is
high spin or low spin.
d.
Place the appropriate number of electrons in the d orbitals and determine
the number of unpaired electrons.
SOLUTION
a.
A With six ligands, we expect this complex to be octahedral.
B The fluoride ion is a small anion with a concentrated negative charge, but
compared with ligands with localized lone pairs of electrons, it is weak field.
The charge on the metal ion is +3, giving a d6 electron configuration.
C Because of the weak-field ligands, we expect a relatively small o, making
the compound high spin.
D In a high-spin octahedral d6 complex, the first five electrons are placed
individually in each of the d orbitals with their spins parallel, and the sixth
electron is paired in one of the t2g orbitals, giving four unpaired electrons.
b.
A This complex has four ligands, so it is either square planar or

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tetrahedral.
B C Because rhodium is a second-row transition metal ion with a d 8 electron
configuration and CO is a strong-field ligand, the complex is likely to be
square planar with a large o, making it low spin. Because the strongest dorbital interactions are along the x and y axes, the orbital energies increase
in the order dz2dyz, and dxz (these are degenerate); dxy; and dx2y2.
D The eight electrons occupy the first four of these orbitals, leaving
the dx2y2. orbital empty. Thus there are no unpaired electrons.
SUMMARY
Crystal field theory (CFT) is a bonding model that explains many properties of
transition metals that cannot be explained using valence bond theory. In CFT,
complex formation is assumed to be due to electrostatic interactions between a
central metal ion and a set of negatively charged ligands or ligand dipoles
arranged around the metal ion. Depending on the arrangement of the ligands, the
d orbitals split into sets of orbitals with different energies. The difference between
the energy levels in an octahedral complex is called the crystal field splitting
energy (o), whose magnitude depends on the charge on the metal ion, the
position of the metal in the periodic table, and the nature of the ligands. The spinpairing energy (P) is the increase in energy that occurs when an electron is added
to an already occupied orbital. A high-spin configuration occurs when the o is less
than P, which produces complexes with the maximum number of unpaired
electrons possible. Conversely, a low-spin configuration occurs when the o is
greater than P, which produces complexes with the minimum number of unpaired
electrons possible. Strong-field ligands interact strongly with the d orbitals of the
metal ions and give a large o, whereas weak-field ligands interact more weakly
and give a smaller o. The colors of transition-metal complexes depend on the
environment of the metal ion and can be explained by CFT.
KEY TAKEAWAY
Crystal field theory, which assumes that metalligand interactions are only
electrostatic in nature, explains many important properties of transition-metal
complexes, including their colors, magnetism, structures, stability, and reactivity.
CONCEPTUAL PROBLEMS
1. Describe crystal field theory in terms of its
a.
assumptions regarding metalligand interactions.
b.
weaknesses and strengths compared with valence bond theory.
2. In CFT, what causes degenerate sets of d orbitals to split into different
energy levels? What is this splitting called? On what does the magnitude of
the splitting depend?
3. Will the value of o increase or decrease if I ligands are replaced by
NO2 ligands? Why?

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4.

For an octahedral complex of a metal ion with a d6 configuration, what

factors favor a high-spin configuration versus a low-spin configuration?

5. How can CFT explain the color of a transition-metal complex?
STRUCTURE AND REACTIVITY
1. Do strong-field ligands favor a tetrahedral or a square planar structure?
Why?
2. For each complex, predict its structure, whether it is high spin or low spin,
and the number of unpaired electrons present.
a.[TiCl6]3
b. [CoCl4]2
3. For each complex, predict its structure, whether it is high spin or low spin,
and the number of unpaired electrons present.
a.
[Cu(NH3)4]2+
b.
[Ni(CN)4]2
4. The ionic radii of V2+, Fe2+, and Zn2+ are all roughly the same (approximately
76 pm). Given their positions in the periodic table, explain why their ionic
radii are so similar.
ANSWERS
3.

a.d9, square planar, neither high nor low spin, single unpaired electron
b. d8, square planar, low spin, no unpaired electrons
EXERCISE
For each complex, predict its structure, whether it is high spin or low spin,
and the number of unpaired electrons present.
a. [Mn(H2O)6]2+
b. [PtCl4]2
ANSWER
a. octahedral; high spin; five
b. square planar; low spin; no unpaired electrons