MAGNETISM

Types of Magnetism

There are four types of magnetism:

(i) Diamagnetism (ii) Paramagnetism (iii) Ferromagnetism (iv)
Antiferromagnetism

Diamagnetism
It is caused by paired, filled shell electrons. It arises from the
motion of the electron. This effect is submerged by unpaired
electron spins.
A diamagnetic material experiences a force in a direction
opposite to that of the magnetic field gradient.
The magnitude of susceptibility is small and negative. It is
approximately equal to –1 x 10-6 cgs units.
This is independent of magnetic field, H and temperature, T.
(e.g.) H2O, KCl, Organic ligands

Paramagnetism
It is caused by unpaired electron spin and orbital motion.
The magnitude is positive and approximately equal to 10 -
100 x 10-6 cgs units.
This is independent of magnetic field, H and varies
inversely with T.
(e.g.) [Cr(H2O)6]SO4, (NH4)2[Mn(H2O)6](SO4)2

Ferromagnetism
Neighboring particles with unpaired spins interacting among
themselves cause this.
The susceptibility is positive and very large and
approximately equal to 10-2 to 104 x 10-6 cgs units.
They may be aligned parallel so that the material possesses
an overall magnetic moment and is ferromagnetic. Above the
Curie temperature, Tc, the gram susceptibility,g, varies
inversely with T. But below Tc, g rises abruptly and
dependent on H.

1
 (e.g.) metallic iron

Antiferromagnetism
Neighboring particles with unpaired spins interacting among
themselves cause this.
The unpaired electrons may be aligned in antiparallel
fashion giving overall magnetic moment and antiferromagnetic
behavior.
The susceptibility is positive, but very small and
approximately equal to 0.1 x 10-6 cgs units.

Effects of Temperature

Curie Law
The law is stated as follows:
“The magnetic susceptibility is inversely proportional to
temperature.
 = C/T
where ‘C’ is the Curie constant.
Many paramagnetic substances obey the simple Curie law,
especially at high temperatures.

Curie – Weiss Law

This law is stated mathematically as follows:
 = C/(T + )
where ‘’ is the Weiss constant.
When -1 is plotted against T, we get the curves as sown in
Figure 1.
-1

Curie – Weiss law Curie law


T(K)

2
 The temperature dependence of various magnetic
susceptibilities are schematically shown below:

3
 For all materials, the effect of increasing temperature is to
increase the thermal energy possessed by ions and electrons.
Therefore, there is a natural tendency for increasing structural
disorder when the temperature increases.
In the case of paramagnetic materials, applied magnetic field
orders the spins of the molecules. But the thermal energy
partially cancels this ordering effect. As soon as the magnetic
field is removed, the orientation of the electron spins becomes
disordered.
Hence, for paramagnetic materials,  decreases with
increasing temperature according to Curie or Curie – Weiss
law fashion.
In the case of ferro- and antiferromagnetic materials, spins
are perfectly arranged as parallel or antiparallel. However,
temperature introduces disorderliness in this arrangement.
Hence, there is a rapid decrease in  with increasing
temperature for ferromagnetic materials.
For antiferromagnetic materials, this leads to a decrease in
the degree of antiparallel ordering. Therefore,  increases.

4
Zeeman Effect
The splitting of levels by the external magnetic field is
called Zeeman effect. This is of two types:
1. First order Zeeman effect
2. Second order Zeeman effect
First Order Zeeman Effect
The effects produced on the ground levels (i.e. splitting of
the levels) by the first power of the magnetic field are called
first order Zeeman effect. That is, the change in energy of the
levels is proportional to H.

Second Order Zeeman Effect

The effects produced on the levels by the second order of
magnetic field are called second order Zeeman effect. That is,
the change in energy is proportional to H2. This is explained as
follows:
When the magnetic field acts on an ion, the electron
distribution is distorted. Therefore, the ground state mixes with
a small amount of some higher state. This mixing is
proportional to the magnetic field, H. this magnetic field and
the consequent mixing lowers the energy of all the components
of the ground state by an amount proportional to H2. This is
called second order Zeeman effect. This effect is illustrated for
Cu2+. The ground state is 2E. That is, the ground state is a
doublet. Both the components of this doublet are lowered by
the quantity cH2:
Cu2+ system

E doublet gH
No field gH
H
1st order cH2
Magnetic field
2nd order
Magnetic field

5
The lowering of energy by the magnetic field, that is, E/H is
linear in H. Therefore the susceptibility remains independent of
the magnetic field.
In other words, when a non-degenerate level lies lowest,
Zeeman effect cannot split it. Therefore, there can be no
contribution to the magnetic susceptibility from the first –
order Zeeman effect. However, if any paramagnetic
susceptibility is present, it is due to the second – order Zeeman
effect.
This happens when kT is less than the energy separation
between the ground level and the higher lying levels. The
susceptibility arising in this way can be very large.

Temperature Independent Paramagnetism (T.I.P)

Thermal distribution between the ground and higher levels
will occur if the separation between them is in the order of kT.
However, if the level that mixes with the ground level lies
much more than kT above the ground level, thermal
distribution between the levels does not occur. Hence, the
contribution made to the susceptibility is independent of
temperature. Therefore it is called temperature independent
Paramagnetism (T.I.P).
In cupric ion, T.I.P is about 60 x 10-6 cgs unit and this adds
to the molar susceptibility of about 1500 x 10-6 cgs units at
room temperature.
Co3+; t2g6, spin paired
This ion should be diamagnetic because there are no
unpaired electrons. Nevertheless, molar susceptibilities of
about 100 x 10-6 cgs units are observed for this ion. It is due to
T.I.P. Here, there is no first order splitting because all the spins
are paired. However, the energy of the singlet ground state is
lowered due to the second order magnetic field and similarly
that of the higher singlet state.

6
Magnetic Moment and Magnetic Susceptibility (eff. And )
Magnetic properties of complexes are discussed in terms of
a quantity called the ‘magnetic moment’, eff. rather than that
of the susceptibility, . Both are related as follows:

eff. = (3k/N2)(aT)
= 2.828(aT)
where eff. Is the paramagnetic moment, ‘k’ is the Boltzmann
constant and ‘N’ is the Avogadro number.
If Curie’s law is obeyed, eff. should be independent of
temperature.
eff. = 2.828(AT)
A = C/T (Curie’s law)
 eff. = 2.828{(C/T) x T)}
i.e. eff. = 2.828 x C

7
The Magnetic Properties of Free Ions
The magnetic properties of free ions depend on the
following factors:
1. First order Zeeman effect
2. Second order Zeeman effect
3. States approximately equal to kT
4. States << kT
1.First order Zeeman effect
Let us consider a system and let the degeneracy of its term
be lifted by spin-orbit coupling. This leads to states. When a
magnetic field is applied, the remaining degeneracy of the
states may be lifted.
Let us consider the ground state, J = 2, and let the other
states lie very much above kT. The first order Zeeman effect
splits the levels according to the relation, WJ = MJgH and the
splitting is shown below:
MJ
2 2gH
1 gH
J = 2 0 0
-1 -gH
-2
-2gH

No magnetic field Magnetic field

The magnetic moment of a system, which consists of ground

state only, is given by Equation (1):

eff. = g[J(J+1)] ---------- (1)

The above equation applies well to most of the lanthanide ions,
where the ground state alone is considered in determining the

8
magnetic properties. In these ions, spin – orbit coupling is so
large that states other than the ground states are thermally
inaccessible. As far as the ‘f’ electrons are concerned, the ions
are essentially free.
The splitting factor, g, is a function of the amount of orbital
and spin angular momenta which the state possesses. If a state
specified by ‘J’ arises from a term specified by L and S, then
S(S+1) – L(L+1) + J(J+1)
g = 1+
2J(J+1)

For a system in which there is no orbital angular momentum,

L=0. Therefore, J=S (because J=L+S; J=0+S; J=S).

S(S+1) – 0 + S(S+1)
 g = 1 +
2S(S+1)

2S(S+1)
i.e., g = 1 +
2S(S+1)
g = 1+1
or , g = 2

In other words, when the magnetic behavior of an ion is due to

the spin angular momentum alone, g = 2. Then from equation
(1), we have,

eff. = g[J(J+1)]
= 2[S(S+1)] (because g = 2 and J = S)
If the number of unpaired electrons in the ion is equal to ‘n’,
then S = n/2.

 eff. = 2[n/2(n/2+1)]
= 2/2[n(n+2)]
= [n(n+2)] --------- (2)

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Equation (2) is called the spin – only formula for the magnetic
moment because they correspond to the contribution from spin
angular momentum alone.
The spin only values for different ‘n’ values are given in
Table 1.

Table 1 Spin – only values

n 2S+1 eff.s.o A
1 2 1.73 1250
2 3 2.83 3333
3 4 3.87 6250
4 5 4.90 10000
5 6 5.92 14600
6 7 6.93 20000
7 8 7.94 26250

When the spin-orbit coupling constant,  , is of the order of kT,

more than one state is thermally accessible. That is, more than
one level can be populated. Now the susceptibility of the
system as a whole is due to the first order Zeeman effect
contribution from each state. This contribution is proportional
to its Boltzmann population.

2. Second order Zeeman effect

When the state having J = 0 lies lowest and that with J = 1
lies >>kT above it, the susceptibility arises from the second
order Zeeman effect alone.

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3. States approximately equal to kT
When there are states separated from the ground state by
energy of the order of kT (kT = 210 cm-1 at 300K), both first
order and second order Zeeman effects from adjacent states
contribute.

Quenching of Orbital Angular Momentum by Ligand

Fields

When a free ion is converted into its complex, there is a

loss in the orbital angular momentum. If the orbital angular
momentum is to exist, two requirements must be satisfied.

Requirement 1
When an orbital can be rotated by about an axis to give an
identical and degenerate orbital, orbital angular momentum
results.
For example, in the free ion, dxz orbital can be rotated about
the z-axis by 90o to give the dyz orbital and vice versa.
Similarly, the dxy orbital can be rotated about the z-axis to give
dx2-y2 orbital. Hence, orbital angular momentum results
between these orbitals.
However, in the presence of a cubic ligand field, the dxy
and dx2-y2 orbitals are no longer degenerate and no orbital
angular momentum results between them. That is, the ligand
field quenches orbital angular momentum. Nevertheless, the
ligand field does not quench all the orbital angular momentum
because the dxz and dyz orbitals remain degenerate.
Orbital angular momentum remains to some extent with
the t2g orbital. The reason is that the rotation about the z-axis
turns dxz into dyz and rotation about the x- or y-axis turns dxy
into dxz or dyz respectively.
However, no rotation can turn the dz2 orbital into dx2-y2
orbital because they differ in shape. Hence, there is no orbital
angular momentum associated with the eg set.

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Requirement 2
A second requirement for the existence of orbital angular
momentum due to orbital rotation is that there should not be an
electron in the second orbital with the same spin as that in
the commencing orbital.
In the configurations t2g0, t2g3 and t2g6, it is not possible to
make the required transformations of the d-orbitals because t2g0
is vacant; t2g3 and t2g6 have no vacant orbital. The configuration
and the corresponding terms are given below:

Configuration Terms

t2g3eg0 4
A2g
t2g3eg1 5
Eg
t2g3eg2 6
A1g
t2g6eg0 1
A1g
t2g6eg1 2
Eg
t2g6eg2 3
A2g
t2g6eg3 2
Eg

All the above configurations do not have orbital angular

momentum. The terms are either A or E. Thus orbital angular
momentum is quenched for A and E terms.
The configurations t2g1egm, t2g2egm, t2g4egm and t2g5egm lead
to T terms. The orbital angular momentum is not completely
quenched. That is, the orbital angular momentum remains for T
terms.

Spin-orbit coupling constant and magnetic moment

If spin-orbit coupling is present, the observed magnetic
moment will be different from the spin-only value.

 and 
The symbol  denotes spin-orbit coupling constant of the
free ion. It is given by the expression,

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 Ze2h2
 =
82m2c2r3

 is the spin-orbit coupling constant of the complex ion.  and

 are related as follows:

 =   / 2S
=/n
where ‘n’ is the number of unpaired electrons. ‘+’ sign applies
to less than half-filled shells and ‘-’ sign applies to more than
half-filled shells.

Magnitude of  or 
The magnitude depends on the following factors:
1.The effective nuclear charge Zeff. When the atomic number
increases, Zeff. increases and  or  increases.
2. Oxidation state. For a given metal ion, an increase in the
positive oxidation state leads to a decrease in ‘r’. Zeff. increases
and  increases.
3. Within a group. Going down the transition series (3d to 4d
to 5d) along a group increases  or . (e.g. (Cr3+) = 275 cm-1,
(Mo3+) = 820 cm-1, (W3+) = 1800 cm-1)
4. The effective orbit radius. In a complex, the effective orbit
radius increases due to electron cloud expansion. Therefore, 
increases. The value of  for a complex ion is 20 – 25% less
than that for a free ion.

In a weak octahedral crystal field, that is, in a high-spin

complex, the number of unpaired electrons is the same as in
the case of free ion. In such a case  will be +ve if the number

13
of electrons is less than five and  will be –ve if the number of
electrons is more than five.
In a strong crystal field, that is, in a low-spin complex, the
t2g orbitals comprise the shell. In a low-spin d4 complex, the
arrangement will be t2g4 and more than half filled and  is
negative.
All the tetrahedral complexes are high-spin. Hence, the sign
of  will be the same as that of the free ion.
For 6A1g, we have an orbital singlet, and therefore, 
becomes redundant (meaningless). Whenever L or S is zero,
there is no spin-orbit interaction and  becomes redundant
(meaningless). Spin-orbit coupling constants (in cm-1) for 3d
transition series metal ions are given in Table 2.

Magnetic moments and multiplet widths

Case 1. Multiplet width >> kT.
In this case, L and S couple very strongly. The two
vectors do not remain distinct. The spin-orbit coupling constant
 must be very high so that L and S vectors interact strongly.
Now the lowest lying component (lowest lying J) alone is
populated. The vectors L and S precess rapidly about the
direction of the resultant vector J. It can be assumed that L
and S also precess rapidly about J. Effectively, LS is
precessing rapidly about J. Finally, LS is given approximately
by J.
J = g[J(J+1)]
From the above equation, equations for L and S are derived
as follows:
When there is only orbital magnetic moment, S = 0 so
that J = L, and hence g = 1.

 L = [L(L+1)]
For the spin-only magnetic moment, L = 0, so that J = S.
 g = 2

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  S = 2[S(S+1)]
= [4S(S+1)]
= [2S(2S+2)]
However, the resultant spin quantum number,
S = ns
= n()
where ‘n’ is the number of unpaired electrons.
 S = [n(n+2)]
S is called the spin-only magnetic moment.

eff. = [M3kT /N]  emu

= [M3kT/N2]
 = eh/4mc
[ erg/gauss = Bohr magneton]

eff. = 2.83(MT) B.M.

Case 2. Multiplet width < kT

When the multiplet width is quite small as compared to
kT, all the J levels may be populated. Now, the coupling of L
and S vectors is insignificant. Therefore, the two vectors
remain distinct. Hence, the magnetic moment is due to the sum
total of the spin and orbital effects.

M = NL2/3kT + NS2/3kT
= N/3kT(L2 + S2)
 = [M3kT/N2]

Substituting the value of M, we get,

L+S = [L(L+1) + 4S(S+1)]

Case 3. Multiplet width  kT

When the multiplet width is comparable to kT, to
calculate the total magnetic susceptibility, the magnetic

15
susceptibility due to each ‘J’ level, along with the population of
the ‘J’ level is to be considered.
The three cases can be summarized as follows:
Multiplet width (B.M.) Temperature
dependence of M
Large g[J(J+1)] 
M  1/T
compared to
kT
Small [L(L+1)+4S(S+1)] M  1/T
compared to
kT
Comparable to Complicated function of Curie’s law not
kT J and T obeyed

Van Vleck Equation

The magnetic property of a paramagnetic substance
originates from the permanent magnetic dipoles present in it.
When a magnetic field is applied the following effects take
place.
(i) the magnetic dipoles tend to align themselves along
the field direction against the opposing influence of
temperature. As a result, the MJ levels of a particular
J are symmetrically split into lower and upper levels.
This splitting is known as the first order Zeeman
effect.
(ii) The orbitals get distorted via the introduction of
some character of the excited state into the ground
state. This is known as the second order Zeeman
effect.

Derivation
In deriving the Van Vleck equation, two
assumptions are made:
(i) the paramagnetic susceptibility is independent of the
applied magnetic field,H.

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 (ii) the energy of the ith level of the atom or ion is a
power series in H. That is,

Wi = W(0) + W(1)H + W(2)H2,

Where Wi(0) is the energy of the ith level in absence of H, and
Wi(1) and Wi(2) are the first order and second order Zeeman
coefficients respectively.
If a substance is devoid of permanent magnetic dipoles,
there is no first order Zeeman interaction with H, which means
Wi(1) will be zero.
A magnetic dipole, when it interacts with the magnetic
field, lowers its energy. The Van Vleck equation is:
N[Wi2(1)/(kT) – 2Wi(2)]e-Wi(0)/(kT)]
M =

eWi(0)/(kT)
The above equation can be segregated as follows:
N[Wi(1)2/(kT)e-Wi(0)/(kT)]
Mfirst order) =

e-Wi(0)2/(kT)

NWi(1)2/(kT) (since Wi(0)=0)

= 2J+1 ------- (1)
where 2J+1 is the multiplicity, i.e., degeneracy of the level
concerned.

-2NWi(2)e-Wi(2)e-Wi(0)/(kT)
M(second order) =
e-Wi(0)/(kT)

-2NWi(2)
= since Wi(0) = 0 ------ (2)
2J+1

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The above equation can be expressed as:
-2NWi(2)
M(second order) = N =
2J+1

2
or  = Wi(2) --------------- (3)
2J+1

Temperature – dependence of Second Order Magnetic

Susceptibility

The first order Zeeman magnetic susceptibility equation(1)

carries kT, whereas the second order Zeeman magnetic
susceptibility equation(2) does not. Therefore, the magnetic
susceptibility due to second order effect is usually independent
of temperature. When the separation of the interacting levels is
small and of the order of kT, the excited level is actually
populated. Hence, only at very low temperatures, the second
order magnetic susceptibility will be independent of
temperature (because higher levels will not be populated).
When the separation of the interacting levels is much greater
than kT, the upper level is not populated and the second order
contribution will be independent of temperature.

Magnitude of Second Order Contribution

The second order Zeeman effect is inversely proportional to
the separation of the interacting levels. This separation is
usually quite large, and so M due to this effect is rather small.
It is usually one order of magnitude smaller than the first order
contribution. The second order contribution is very important
in a complex with no spin magnetic moment. If the separation
is large, mixing is small and second order contribution will be
less.
The overall sign of M(second order) is positive.

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Relation of Second Order Magnetic Susceptibility to Curie
Law
The second order M is not inversely proportional to ‘T’. It
is a constant term. The magnetic moment derived from the
second order effect will be a function of T.
Consider the relation,M = N22/(3kT). When ‘T’
decreases, M should decrease. But it is a constant. Therefore,
to maintain M a constant  should decrease. Constant N is
added to the magnetic susceptibility as a correction term. (This
constant should not be used as a variable parameter.)

 M = N22/(3kT) + N

Effect of Magnetic Field on Second Order Magnetic

Susceptibility
The second order magnetic susceptibility, M depends on
the magnetic field, H. When H = 0, the second order effect
vanishes. Hence, second order magnetic susceptibility is an
induced effect like diamagnetism. However, unlike
diamagnetism, it makes a positive contribution to M(first
order). Its magnitude is of the same order as that of
diamagnetism.

Other Names for Second-Order Magnetic Susceptibility

The other names for second-order magnetic susceptibility
are:
(i) Temperature – independent Paramagnetism (T.I.P)
(ii) Van Vleck Paramagnetism
(iii) Residual Paramagnetism

Ground State Diamagnetic (S=0) and Induced

Paramagnetism
When the ground state is diamagnetic (S=0), even a mixing
with the excited state terms via spin – orbit coupling cannot
generate paramagnetic susceptibility. However, paramagnetism

19
can be induced via mixing of the ground state and the excited
state, which is capable of making an orbital contribution, under
the influence of a magnetic field. This is the case with low-
spin (t2g6; diamagnetic) cobalt(III) complexes and d0 systems
like KmnO4 and K2CrO4. The ground state in such instances is
spin and orbital singlet, and the excited state is several times
kT above the ground state. The T.I.P for an octahedral
cobalt(III) complex can be calculated using the formula,

2 eh 24 4.085
T.I.P = N( ) =
3 2mc D D
1 1
where ‘D’ is the energy of the A1g T1g transition and is
obtained experimentally.
The ratio of the experimental T.I.P. and the theoretical
T.I.P. gives k2, where ‘k’ is the orbital reduction factor.
A ‘k’ value in the range 0.5 – 0.9 indicates the covalent
nature, and a ‘k’ value of ‘1’, the ionic nature of a complex.
A high – spin d5 system (Fe3+ and Mn2+) has the 6A1g
ground state term in an octahedral field. This term is an orbital
singlet and has no orbital angular momentum. Such a system
has no excited term with the spin multiplicity six. Therefore,
there is no mixing and has no second order Zeeman effect.

Spin – Orbit Coupling on A, E and T terms

There is no orbital rotation in the A and E terms. That is,
one orbital cannot be converted into another by any symmetry
operation. Hence, there is no orbital magnetic moment in the A
and E terms. But the T term has orbital rotation. That is, dxz
orbital can be converted into dyz orbital by rotation through 90o
about the z-axis. Hence, orbital magnetic moment is present in
the T terms.
However, the orbital magnetic moment maybe brought into
the A and E ground state terms from the excited T terms via
spin-orbit coupling.

20
Magnetic Moment and 10Dq
The magnetic moment and 10Dq obtained from the
electronic spectrum can be quantitatively connected as follows:
g = 2 for spin only system.
For 3A2g term,
g = 2 - 8/(10Dq)
= 2[1-4/(10Dq)]
eff. = 2[1-4/(10Dq)][S(S+1)]
= [1-4/(10Dq)]s (because s = 2[S(S+1)])
This equation quantitatively connects the magnetic moment
and 10Dq obtained from the electronic spectrum. Depending
the sign of , the eff. values may be higher or lower than the s
values.
Sign of :
 is +ve for less than half full shells and  is –ve for more
than half full shells.
Example:
d7 tetrahedral cobalt(II) has ground state 4A2 and d8
octahedral nickel(II) has ground state 3A2g. These have more
than half full shells. Therefore,  is –ve and therefore eff.>s.
d3 chromium(III) octahedral has ground state 4A2g and  is
positive because it is less than half full. Therefore, eff.<s.

For a d5 octahedral system, the Russell – Saunders term in

the absence of a magnetic field is 6S and the corresponding
spectroscopic term is 6A1g. It is an orbital singlet term and
hence, has no orbital angular momentum associated with it. In
addition, there is no other term having the same multiplicity as
6
A1g. Therefore, interaction via the spin-orbit coupling or via
the second order Zeeman effect is not possible. Therefore, the
observed magnetic moment of the system is due to the s only.

For a low-spin octahedral d6 system [cobalt(III)] , the

ground state term is 1A1g and the complex is diamagnetic. But
there is interaction with the excited state terms, 1T1g and 1T2g

21
due to the second order Zeeman effect. These excited state
terms have orbital contribution. Hence, a positive molar
susceptibility arises to the extent of +100 x 10-6 cgs units. But
no spin-orbit coupling can occur since the ground state term
and the excited state terms are diamagnetic. ( All are singlet
terms; 2S+1 =1; S = 0, that is completely paired and hence
diamagnetic.). The second order Zeeman susceptibility is given
by 8N2/(10Dq)

Octahedral high-spin d4, low-spin d7 and d9 configurations

have E ground state terms. The spin-orbit interaction of an E
term with a higher energy T2 term having the same multiplicity
as that of the E term, gives the ‘g’ value as follows:

g = 2[1-2/(10Dq)]
eff. = [1-2/(10Dq)]s
For the tetrahedral complexes of vanadium(IV),  is +ve, so
that eff.<s. For the octahedral complexes of copper(II),  is –
ve, so that eff.>s

Spin-orbit coupling on T terms

T terms retain orbital angular momentum. Therefore, the
actual magnetic moment will exceed s.
Example:
Hexaaquotitanium(III) sulphate - d1 system.
2
Eg

2
D 
2
2
T2g J=
0
-/2
J=3/2
g

22
In order to calculate the L,S and J values, correspondence
between the p and t2g orbitals must be arrived at. It can be
shown that the orbital angular momentum integrals of the
members of the ‘p’ orbital set are equal in magnitude but
opposite in sign to those of the corresponding members of the
t2g set. Therefore, l = 1 for the T terms and there is a negative
correspondence between the ‘p’ and t2g orbital sets. For the T
terms, the t2g is less than half full. Therefore J with higher
value will be the lower energy state. Considering the 2T2g term,
S = ; L= 1; J = L+S = 1+ = 3/2
J can have values L+S , L+S-1, L+S-2 -------- , L-S and in this
case 3/2 and . The lower level will have J = 3/2.
Lande Interval Rule
The energy difference between two successive J levels
is given by the product of  and the larger of the two J values.
In this case larger value of J = 3/2. Therefore, the energy
difference = 3/2.
Importance of this rule
In most substances, the magnetic properties originate
from the ground state ‘J’level. But sometimes the first, or even
the second excited state may be significantly populated. In such
cases, we should know the energy separating the excited and
the ground state.
For the above titanium(III) complex, d1 system,  =
+155cm-1 and the energy separation between the two J levels is
equal to 3/2 = 3/2 x 155 = 232.5cm-1. The value of kT at
300K is equal to 0.69504cm-1 x 300 = 208.5cm-1 because kT at
1K = 0.69504cm-1. Thus the energy separation between the two
J levels is in the range of kT.
g(t2g) = -1 + 3[J(J+1) + S(S+1) – L(L+1)]/[2J(J+1)]
For J = 3/2,
g = -1+3[3/2(3/2+1)+(+1)–1(1+1)]/[2 x 3/2(3/2+1)]
= -1+1 = 0
The –ve sign is introduced to show the negative
correspondence between the t2g set and ‘p’ orbitals and ‘3’ is
introduced because the degeneracy is ‘3’.

23
 Similarly it can be shown that g = 2 for J =  state.
Since g = 0 for the ground state, magnetic property will not
arise from this state. Therefore, M will arise from the second
order Zeeman effect. Then the magnetic property will be
independent of temperature. When the temperature is
increased, the higher level, J = H, will be populated. For this
level, g0. Hence, this level has first order Zeeman effect.
Therefore, M is dependent on temperature.
The above figure is also applicable to a tetrahedral 3d9
copper(II) complex. This also has 2T2 ground term. But for
copper(II),  = -830 cm-1 and J is –ve. Therefore, J =  level
becomes the ground state and g  0 for this level. Hence, this
level shows first order Zeeman effect and M is temperature
dependent.
As the temperature decreases, this level will be populated
more so that  approaches S = 1.73 B.M., since g = 2. When
the temperature increases, J = 3/2 level will be populated. This
level ( g= 0) experiences second order Zeeman effect. Hence,
the susceptibility will be due to the spin – only contribution
and the second order Zeeman effect.

3d2 configuration (3T1g term)

For the 3T1g term, L = 1 because there is correspondence
between p orbital set and t2g set, though –ve, S = 1 and J is
found out as follows:
J = L + S = 1+1 =2; L – S = 1-1 = 0.  J = 2,1,0.
Because of the –ve correspondence between the t2g and p
orbitals, the ground state for the d2 system will be J = 2 and the
first excited state will be J = 1 and so on.
The energy gap between the successive levels is given by
the Lande interval rule, that is, the product of  and the larger
of the two J values. Thus, the difference between the J = 2 and
J = 1 states is 2A, where A = (1.5 – c2)/(1 + c2) and ‘c’ is the
mixing coefficient.
c = (6Dq + E)/(4Dq)

24
g is obtained as a complicated function in A.
(e.g.) Octahedral vanadium(III) complex.
The ground state term is 3T1g. For V(III),  = +105 cm-1.
Using this value, the Van Vleck equation predicts  = 2.7 B.M.
at 300 K. This should decrease with the fall in temperature till
 = 0.62 B.M. at 0 K. Actually, ammonium vanadate(III)
alum records  = 2.7 B.M. at 300 K as well as at 80 K. That is,
 is temperature independent. The reason is that this does
compound does not possess a truly octahedral geometry but
belongs to a low symmetry. This low symmetry destroys the
orbital angular momentum associated with the T term. If this
splitting by the low symmetry is larger than that due to the spin
– orbit coupling, then  will tend to approach s and its
temperature dependence will not be significant.

(e.g. 2) K3[Mn(CN)6] ; low-spin ; d4 system

The ground state term is 3T1g.  - 3.50 B.M. at 300 K and
3.31 B.M. at 80 K. The magnetic moment rapidly decreases to
zero at 0 K. Thus the magnetic moment is temperature
dependent. This shows that the orbital angular momentum is
not destroyed. (Oh symmetry). The higher levels are also
populated and hence the higher levels also contribute to
magnetic moment. The extent of population depends on
temperature. As the temperature is lowered, the population also
decreases. Hence, contribution to magnetic moment also
decreases.

Electron Delocalisation and Consequent Effects on

Magnetic Properties
There is always some overlap between the metal and ligand
orbitals. This leads to electron delocalisation and this must be
considered to get an agreement with the experimental results.In
such cases, the orbital angular momentum is reduced by a
factor ‘k’, called the delocalisation factor. When k = 1, there is
no delocalisation. In a covalent complex, it is less than unity.
For A2g term,

25
 g = 2[1 – 4k2/10Dq]
eff. = S[1 – 4k2/10Dq]
M (second order) = 8k2N2/10Dq
For Eg term,
g = 2[1-2k2/10Dq]
eff. = S[1 – 2k2/10Dq]
M(second order) = 4k2N2/10Dq
The total magnetic susceptibility is given by the sum of the
first and second order effects.

M(A2g) = M(spin–only)[1 – 8k2/10Dq] + 8k2N2/10Dq

M(Eg) = M(spin-only)[1 – 4k2/10Dq] + 4k2N2/10Dq

Examples:
1. [Ni(H2O)6]SO4

M = 4340 x 10-6 cgs units at 300 K

From electronic spectrum,
10Dq = 8900 cm-1 corresponding to the transition
3 3
A2g T2g
For free ion  = -315 cm-1
Second order Zeeman coefficient,
8N2/10Dq = 235 x 10-6 cgs/mol
(N2 = 0.261 cm-1 erg/gauss2 mol)
M(A2g) = M(spin-only)[1 – 8k2/10Dq] + 8k2N2/10Dq
4340 x 10-6 = [3333(1+8 x 315k2/8900) + 235k2] x 10-6
k = 0.93
The value of ‘k’ indicates that the degree of delocalisation of
the ‘d’ electrons of the metal ion is small.

2. [Cu(H2O)6]SO4. K2SO4

The ground state term for Cu(II) is 2Eg

M = 1520 x 10-6 cgs units at 300K

26
10Dq = 12000 cm-1 corresponding to the transition,
2 2
Eg T2g
For free ion,  = -830 cm-1
M(Eg) = M(spin-only)[1 – 4k2/10Dq] + 4k2N2/10Dq

1520 x 10-6 = 1250{1+(4k2 x 830)/12000}

+ (4k2 + 0.261/12000) x 106]x10-6
k = 0.69
This shows that the delocalisation of the metal ‘d’
electrons is significant.

27
 Anomalous Magnetic Moments

When the magnetic moment for a metal ion falls outside the
range of predicted value based on the spin angular and orbital
angular momenta of electrons, it is called anomalous value.

Discrete molecular species (Magnetically dilute)

Here, there is no secondary magnetic interaction between

the neighboring molecules. That is, there is no ferromagnetic or
antiferromagnetic interaction in these systems. That is, the
systems are magnetically dilute.
(e.g.) Nickel(II) complexes
In the octahedral symmetry, the ground state term is 3A2g
and it acquires some orbital contribution from the 3T2g excited
term due to spin-orbit coupling. The overall magnetic moment
is dependent on 10Dq and  as follows:
eff. = S(1-/10Dq)
where  = 4 for the A term and 2 for the E term.

Reasons for anomalous magnetic behavior

1. Equilibrium between two spin states.

2. Magnetically non-equivalent sites in the unit cell.
3. Solute-solvent interaction.
4. Solute-solute interaction.
5. Configurational equilibrium.

1. Equilibrium between two spin states

There may be equilibrium between high-spin and low-spin
states in certain cases. For example, in the octahedral
geometry, when the crystal field strength is in the region of the
critical 10Dq, a spin state equilibrium may arise for the d4, d5,
d6 and d7 configurations. But it is not so in the case of 3d8
nickel(II) octahedral complexes because the 3A2g ground state

28
term and 1Eg excited state terms are almost parallel at all
crystal field strengths.
But if there is a tetragonal distortion of an octahedral
geometry, the spin-state of nickel(II) complex may change.
This distortion will take place if the complex is a mixed ligand
complex like Nia4b2. The ligands are present in axial positions.

b1g x2-y2

b1g
eg 2
a1g 1

b2g xy

3d a1g z2

b2g

t2g
eg

eg xz,yz

Tetragonal Distortion of Octahedral Complex

If the ligands a and b have similar crystal field strengths, 1

and 2 will be small.  will be approximately equal to 3.0 B.M.
But if ‘b’ is a very weak ligand compared to the ligand ‘a’,
1 or 2 may be higher than the pairing energy, P (z – out
distortion). Therefore pairing takes place resulting in
diamagnetism. Hence, when 1 or 2 is in the range of pairing
energy, P, there will be a spin state equilibrium in a tetragonal
nickel(II) complex.

29
(e.g.) Dichlorotetrakis(N,N-diethylthiourea)nickel(II)
This complex is spin-paired below 194 K and  = 0. It
becomes partially paramagnetic when the temperature is
increased. Nickel(II) has a tetragonal field and the magnetic
property is decided only by the thermal population of the two
spin-states. The equilibrium is represented as follows:
Singlet(low-spin) triplet(high-spin)
The equilibrium constant,
[triplet] [high-spin]
K= =
[singlet] [low-spin]
‘K’ is calculated from the knowledge of the mole fractions,
Nlow-spin and Nhigh-spin
The relation between M and mole fraction is given by the
following expressions:
M(expected) = Nlow-spinM(low-spin) + Nhigh-spinM(high-spin)
(Nlow-spin + Nhigh-spin = 1)
The above expression can be expressed in terms of magnetic
moment as follows:

expected2- low-spin2
K=
high-spin2-expected2
Difference between affixed mixture of two spin states and spin-
state equilibrium
Anomalous magnetic moment can also arise from a fixed
mixture of two spin-states(say S=0 and S=1). Now a linear
Curie-Weiss plot will still be obtained for the S = 1 state.
But if the spin-state equilibrium is temperature dependent,
the composition of the mixture will change with a change in
temperature. Now the Curie-Weiss plot will be non-linear.
Thus, form the nature of the Curie-Weiss plot, it is possible
to distinguish between
(i) a fixed mixture of two spin – states and
(ii) a spin-state equilibrium between two spin-states.

30
 In an octahedral crystal field, the spin-state equilibrium is
possible for the following configurations:

d4 t2g3eg1 – 5Eg; t2g4- 3T1g Cr2+; Mn3+

d5 t2g3eg2 – 6A1g; t2g5 – 2T2g Mn2+; Fe3+

d6 t2g4eg2 – 5T2g; t2g6 – 1A1g Fe2+; Co3+

d7 t2g5eg2 – 4T1g; t2g6eg1 – 2Eg Co2+

In each of the above configurations, around the cross-over

region, the energies of the two spin states differ by  kT.
Therefore, the relative populations of the two states vary with
temperature.

Plot of K Vs. 1/T

K is the equilibrium constant between the two spin-states.

If the plot of lnK versus 1/T for a complex is a straight line, it
means that the modification of the crystal lattice does not
influence the magnetic property.
If the plot of lnK versus 1/T for a complex is not a straight
line, it means that the modification of the crystal lattice
influences the magnetic property in addition to the spin-state
equilibrium.

2.Magnetically non-equivalent site in the unit cell

In a unit cell, two situations may arise.
(i). The metal ions may have the same coordination number,
the same set of ligands but different geometries, and
(ii). The metal ions may have different coordination numbers
and hence different geometries.
Example for situation 1.

31
 The complex, dibromobis(benzylphosphine)nickel(II) is
green colored and exhibits an anomalous magnetic moment
of 2.7 B.M.
The X-ray crystallographic study of this compound has
revealed that the unit cell has three nickel(II) complexes –
one square planar and two tetrahedral.
Considering that square of the magnetic moment is
additive and also the mole fractions of the different
complexes, we get,

2 = 0.33 x 2Ni2+(square planar) + 2 x 0.33 x 2Ni2+(Td)

[Square planar : Tetrahedral = 1:2

Total number of moles = 3
Mole fraction of square planar = 1/3 = 0.33
Mole fraction of Td = 2/3 = 2 x 0.33]

2.72 = 0.33 x 0 + 2 x 0.33 x 2Ni2+(Td)

Ni2+(Td) = 3.3 B.M.

Example for situation 2.

A complex has a magnetic moment of 2.58 B.M. The
unit cell of this compound was found to contain one 4-
coordinate square planar nickel(II) complex and two 6-
coordinate pseudooctahedral nickel(II) complexes.

3. Solute – solvent interaction

Anomalous magnetic moment may also arise when a

particular complex interacts with a coordinating solvent. Thus
many square planar diamagnetic nickel(II) complexes become
partially paramagnetic due to an equilibrium of the following
type:
Solvent + Square planar complex(dia) = pseudooctahedral
Complex(para)

32
4.Solute – solute interaction
When two or more molecules of a complex are associated,
coordination number of the metal – ion increases. This
interaction changes the spin-state of the metal ion.
(e.g.) Bis(N-methylsalicylaldiminato)nickel(II)

R H

O N C

Ni

C N O

H R

This is diamagnetic in the solid state. But in soluion, this shows

anomalous magnetic moment in the range 1.9 – 2,3 B.M. This
value depends on the nature of the non-coordinating solvent.
This behavior is not due to planar tetrahedral equilibrium
because the complex has zero dipole moment in benzene or
dioxan.
When the concentration of the complex is increased in
these solvents, the m.wt and magnetic moment also increase,
indicating the presence of solute – solute interaction. When a
substituent is introduced in the ortho position, the complex is
no longer paramagnetic. That is, the solute – solute interaction
does not take place due to steric hindrance.

5.Configurational equilibrium
Octahedral square planar equilibrium also gives rise
to anomalous magnetic moment.

33
 Antiferromagnetism and Ferromagnetism

(Magnetically concentrated system)

When the neighboring magnetic centers are close enough,

direct or indirect overlap of orbitals takes place. Now the
magnetic exchange interaction takes place. This interaction
affects the magnetic property of the complex. Almost all
paramagnetic compounds are involved in exchange interaction
to a certain extent. This interaction is dominant only at a very
low temperature. When the exchange interaction energy is
greater than kT, both ferromagnetism and Antiferromagnetism
jointly operate. Because of the exchange interaction, the
magnetic moment may be more or less than that of a complex
not involved in exchange interaction.
Ferromagnetic interaction increases the magnetic moment
of a complex while antiferromagnetic interaction decreases the
magnetic moment.

Antiferromagnet
The neighboring magnetic centers are opposed to each
other ( ).

Ferromagnet
The neighboring magnetic centers are aligned parallel ( )
Ferromagnetism is rarely encountered but much more useful
than Antiferromagnetism.

Types of Antiferromagnetism
There are two types, viz., intramolecular and intermolecular
Intramolecular Antiferromagnetism
In this type, the interacting paramagnetic centers are
present within the same molecule, which may be dimeric or
polymeric.
(e.g.) Copper(II) acetate monohydrate dimmer,
Cu2(CH3COO)4.2H2O

34
The room temperature magnetic moment per copper(II) ion is
1.4 B.M. But if there were no interactions,  > S = 1.73 B.M.
That is, the magnetic moment is decreased due to
antiferromagnetic exchange interaction.
K4[Ru2Ocl10] ; K4[Cl5Ru – O – RuCl5]
This complex is diamagnetic due to the coupling of
neighboring spins. A monometallic low-spin Ru(IV), d4
complex is expected to exhibit two unpaired spins.

Intermolecular antiferromagnetism

A weak intermolecular antiferromagnetism occurs in many

transition metal complexes. This effect may be found out by
measuring the magnetic susceptibility in solution and in solid
state. The effect will differ.

Antiferromagnetic exchange pathways

The exchange may take place by any one of the following

two methods:
1. Direct metal – metal interaction via overlap of suitable
metal orbitals.
2. Super exchange arising from the transfer of
paramagnetic spin density from one metal ion through
the orbital overlap of the diamagnetic bridging atoms to
an adjacent metal ion.

Direct metal-metal interaction

If the complex has a suitable structure, the metal
orbitals carrying the unpaired electrons may overlap.
Copper(II) acetate monohydrate is a dimmer both in the solid
state and in solution. In this complex, the two copper atoms are
2.64 Å apart. In metallic copper, the Cu-Cu distance is 2.65 Å.
This structure allows a lateral overlap of the dx2-y2 orbitals of
each of the two copper(II) ions, generating a  bond. The ‘d’

35
orbital electron distribution and the energy order of the ‘d’
orbitals in this complex are given below:
dxy( ) < dxz( ) < dyz( ) <dz2 ( ) < dx2-y2 ( )

The unpaired electron resides in the dx2-y2 orbital (2B1 state).

The  bond is shown below:

But if the acetate groups are substituted, Cu-Cu distance is

longer ( 2.69 Å) than that in the metallic copper (2.65 Å) and
hence direct interaction may not be possible.

Mn2(CO)10 is diamagnetic. The oxidation state of

manganese in this complex is zero. An overlap of the two
hybrid orbitals of the two adjacent Mn(0) containing the
unpaired electron leads to diamagnetism.

Superexchange
The super exchange phenomenon usually involves
three atoms. In most coordination complexes, the shell of the
ligands surrounding the metal ion is such that a long metal-
metal distance is usually maintained. This prevents direct
interaction between the metal ions. The system is similar to
magnetically dilute system. But in a magnetically concentrated
system, the metal-metal distance will be usually short and
direct interaction will take place or the bridging ligand atoms
successfully transmit the interaction between the magnetic
dipoles.
In superexchange, suitable partially filled metal
orbitals overlap with a filled ligand orbital. The overlap may be

36
 or -type. In some cases both types of overlap may take
place.

-overlap
In this case each metal ion, M, has one unpaired electron in
its dz2 orbital. The filled ligand orbital is pz. Linear overlap,
that is, -overlap takes place.

-overlap
The unpaired electron will be present in the dxz orbital of
each metal ion. The filled ligand orbital will be px. Lateral
overlap, that is, -overlap takes place.

Antiferromagnetic binuclear complexes

S =  system ; copper(II)
The magnetic exchange interaction in copper(II)
acetates may depend on two factors, namely,
 The metal – metal distance
 The electron – density

37
 Antiferromagnetic interaction is inversely proportional to
the metal – metal distance. That is, when the metal – metal
distance is short, the interaction will be greater.
When the ligand supplies more electron density to the
metal, the antiferromagnetic interaction will be greater.

Interaction through -bond or superexchange

In the case of copper(II) acetate monohydrate, exchange

interaction increases with increase in Cu-Cu distance. This
means that the interaction does not occur through direct metal –
metal bond but occurs through super exchange via carboxylate
bridges. The complex also does not exhibit any electronic
spectral band characteristic of metal-metal interaction.
The super exchange interaction depends on the angle
between the high-spin metal ions.

38