Topic III

Magnetism
Transition & Lanthanide ions
and their complexes
Dr. Deepti Kalsi
 Various contributions to magnetic moment
Magnetic moment

Electron spin Electron Nuclear spin

orbital motion

µorbital

µnuclear µspin
e-

➢ Each of these magnetic fields interact with one another

and with the external magnetic fields.
➢ However, some of these interactions are strong, some are
weak and some are negligible.
 Classes of Magnetism
Two fundamentally different types of response:
a) Diamagnetism - M and  are negative
b) Paramagnetism - M and  are positive

 = D + P
Molecules with paired and unpaired e-‘s = "paramagnetic“
Molecules with only paired e-‘s = "diamagnetic"

Repulsion …… attraction 3
Lighter …… heavier
Dia and Paramagnetic compounds
N2 diamagnetic

Dia.M. ex. H2O, KCl organic ligands,

etc.
Bismuth metal (most diamagnetic
of all metals)

4
O2 paramagnetic
when dioxygen is in its ground state it is a triplet (spin S=1)
and its reactivity is weak.

Liquid O2

5
Video Magnetic Levitation: Property of diamagnetic molecules-I

Courtesy:https://www.youtube.com/watch?v=g4lW7xydnH8
Magnetic Susceptibility
 Curie’s Law
C
M = where C = constant
T
or
N 2 2
C = T = g S ( S + 1)
3k
3k
 so = T = 2.828 T
N 2
Where k = Boltzmann constant
 = Bohr Magneton
 so = g 2 S ( S + 1) = n(n + 2) N = Avogadro’s number
Notes:
1. is a fundamental property of magnetic materials
…..while so (B.M) is arbitrarily derived from .
2. If so is constant with changing temperature
……then  must increase as T is decreased.
3. so can be easily related to the total spin S of a molecule,
……thus linking magnetic measurements to molecular properties.
 Quantum response to H

Quantum model – an electronic state with total spin angular

momentum S has 2S+1 sublevels with spin quantum numbers ms

These levels are degenerate unless a magnetic field is applied, or

they couple with other states

The application of a magnetic field leads to a Zeeman splitting in

the 2S+1 ms levels, each with energy
g  2.0023 (for a free electron)
msgBH B is the Bohr magneton
H = magnetic field
This is the first order Zeeman effect (ZE)
– the splitting is proportional to H
The splitting of levels by the external magnetic field is called
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Zeeman effect.
 The Zeeman effect: s= ½
The application of a magnetic field leads to a Zeeman splitting in
the 2S+1 ms levels, each with energy
g  2.0023 (for a free electron)
msgBH B is the Bohr magneton
H = magnetic field

The difference in populations of ms levels is crucial in providing the magnetization (M) 10

that we measure.
 The Zeeman effect: S= 2

Example: d4- high-spin

12
 The Curie-Weiss Law
Later experiments showed that not all paramagnetic materials obey
Curie’s Law. Some materials have susceptibilities that can be fitted to
the equation:
C
M = zJS ( S + 1)
(T −  ) =
= Curie-Weiss constant. 3k
Weak, inter-molecular interactions are the usual cause of .
z= number of nearest neighbour interactions
J= int. between nearest neighbour
(exchange coupling; not to confuse with J quantum number.

intercept on temperature axis = 

 > 0 for ferromagnets

 < 0 for antiferromagnets

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 Antiferromagnetism
• J negative with spins antiparallel below TN

Paramagnetic
behaviour (PM)

Antiferromagnetic
behaviour AFM

TN T
14
 Ferromagnetism
Spins parallel below Tc

χ
Ferromagnetic
behaviour (FM)

Paramagnetic
behaviour (PM)

Curie Point T
15
 Ferrimagnetism
• Spins of unequal magnitude antiparallel below critical T



Paramagnetic
FiM behaviour

 T
16
e.g. CrF3
TN=-193 °C e.g. Fe
TC = 768 °C

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Magnetic coupling: Origin of AF interaction
Orbital contribution to magnetic moments

• [Ti(H2O)6]3+ shows zero magnetic moment at very low temperatures, why?

 Orbital Contribution to the Magnetic Moment

µtotal

µorbital

µspin
e-

This equation is valid only if L and S are independent of each other.

But what if they are not independent?
How do you determine, if L and S are coupled?
 Spectroscopic Terms (Term Symbols)
Different microstates exists for the same electronic configuration. Free ions
2 1 0 -1 -2

For one unpaired electron in d orbital there are 10 possible microstates. These 10
states are degenerate and are called 2D term.

Russel-Saunders coupling is used to describe the terms. The symbol will represent
the total value of azimuthal quantum numbers (L =  li) and it takes the letters, ‘S, P, D,
F, G’ respectively for L values of 0, 1, 2, 3 and 4.

The degeneracy (2S+1) {S = sum of all the spins} is shown on the left superscript.
The term symbol is shown as (2S+1)L {for eg., 3F corresponds to S = 1 and L = 3}
Number of microstates for 3F is, (2S+1) x (2L+1) = 3 x 7 = 21
 Determination of ground state J
J = L+S, L+S-1………………….. |L-S| Free ions
Most stable term = Ground State Term
Determine the number of 3d electrons in the ion

Rule 1: for a given electronic configuration, the state with highest S is lowest in
energy

Rule 2: for a given electronic configuration and subject to Rule 1, the state with
highest L is lowest in energy

Rule 3: for a given electronic configuration and subject to Rules 1 and 2, the state
with highest J is lowest in energy for ions with a greater than-half-filled 3d sub-
shell; converse true for ions with a less than half-filled shell.
 Ground terms for dn configurations
ml ML=ml Free ions
Configuration Example 2 1 0 -1 -2 L S Ground Term
1 3+ 2
d Ti 2 1/2 D
2 3+ 3
d V 3 1 F
3 3+ 4
d Cr 3 3/2 F
4 3+ 5
d Mn 2 2 D
5 2+ 6
d Mn 0 5/2 S
6 2+ 5
d Fe 2 2 D
7 2+ 4
d Co 3 3/2 F
8 2+ 3
d Ni 3 1 F
9 2+ 2
d Cu 2 1/2 D

Ground Term = (2S+1)LJ

Where the maximum value of ML defines L
L=0, 1, 2 and 3 corresponds to S, P, D and F Terms
Where the maximum value of MS defines S 23
 For lighter elements 3d series: Term Symbols)
The degeneracy (2S+1) {S = sum of all the spins} is
shown on the left superscript.
Ground state symbol = 2S+1 L J
for a d2 system: 3F corresponds to S = 1 and L = 3}
J = (L+S)…………(L-S)

=
Calculate term symbol for Ni+2

Calculate term symbol for V+3

 Ground terms for dn configurations
ml ML=ml Free ions
Ground Term
ConfigurationExample 2 1 0 -1 -2 L S J
1 3+ 2
d Ti 2 1/2 3/2 D3/2
2 3+ 3
d V 3 1 2 F2
3 3+ 4
d Cr 3 3/2 3/2 F3/2
4 3+ 5
d Mn 2 2 0 D0
5 2+ 6
d Mn 0 5/2 - S
6 2+ 5
d Fe 2 2 4 D4
7 2+ 4
d Co 3 3/2 9/2 F9/2
8 2+ 3
d Ni 3 1 4 F4
9 2+ 2
d Cu 2 1/2 5/2 D5/2
Ground Term = (2S+1)LJ
Where the maximum value of ML defines L
L=0, 1, 2 and 3 corresponds to S, P, D and F Terms
Where the maximum value of MS defines S 26
Na D line
Orbital contribution to magnetic moments in the
Presence of ligand field

• First row transition metal ion in octahedral ligand field?

Recap
 Conditions to exhibit orbital angular momentum (µL)
Octahedral field
Rule #1: The orbitals should be degenerate (t2g or eg).

Rule #2 The orbitals should be similar in shape and size. Should be possible to
transform an orbital into an equivalent one by rotation. This is indeed possible to
transform the t2g orbitals into each other by 90o rotation. Such transformation is not
possible with the orbitals of eg.

Rule #3: The orbitals must not contain electrons of identical spin during this
transformation and the movement of electron

➢ These conditions are fulfilled only when one or two orbitals contain partially
filled electrons in t2g and NOT in eg
 Octahedral complexes
Octahedral field
➢ The degenerate t2g orbitals (dxy, dxz, dyz) can be interconverted by 90° rotations.

e.g. the dxz orbital is transformed into the dyz orbital by a rotation of 90°
about the z-axis – during this rotation the electron is orbiting the nucleus

➢ Thus, an electron in a t2g orbital can contribute to orbital angular momentum.

x
y

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 Octahedral field

dyz
dxz
z z
z
x x
dyz 90o rot. x 90o rot.

y
y
y
dxz / dyz orbital motion about z axis
dxz / dxy orbital motion about x axis
dyz / dxy orbital motion about y axis 31
 Octahedral complexes

However the eg orbitals (dz2 and dx2-y2) cannot be interconverted by rotation as they
are different in shapes

Thus an electron in an eg orbital can not contribute to orbital angular momentum.

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 Orbital contribution to the magnetic moment
high spin octahedral dn ions
think of possible t2g electron arrangements

d1 dxz dyz dxy dxz dyz dxy dxz dyz dxy

Possible t2g arrangements = 3 d1 e.g. Ti(III)

Orbital contribution = YES

d2 dxz dyz dxy dxz dyz dxy dxz dyz dxy

Possible t2g arrangements = 3

d2 e.g. V(III)
Orbital contribution = yes 33
But, electrons in t2g orbitals will not always contribute to orbital angular
momentum
e.g. consider octahedral Cr(III) d3, t2g3
an electron in the dxz orbital cannot by rotation be placed in e.g. the dyz
orbital because this orbital already contains an electron with the same
spin as the incoming electron

dxz dyz dxy dxz dyz dxy

Therefore, there is only one possible t2g arrangement,

and NO orbital angular momentum
34
HS
LS 4
HS
LS 5
HS
LS 6
HS
LS 7

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Orbital contribution to the magnetic moment: Excited state(s) contribution

think of possible t2g electron arrangements

Ni(II) d8
t2g filled t2g not comp.
filled
Possible t2g arrangements = 1 Excited state
Orbital contribution = NO

d8 high spin ES

Possible t2g arrangements = 3

Orbital contribution = YES
μexp > μs for Oct. Ni2+ 36
Therefore for Oh Ni(II) the magnetic moments are larger if the GS-ES gap is small. Tetrahedral field
BUT FOR Tetrahedral Ni(II) situation is entirely different ….

d8 HS Tetrahedral

Possible t2g arrangements = 3

Orbital contribution = YES

Μexp Oh Ni(II) is smaller than Μexp Td Ni(II)

Exp. NiCl42-, Ni(HMPA)42+ (HMPA=hexamethyl phosphoramide) have mag. moment

larger than 4 BM. (Larger the distortion smaller the mag.moment )

USEFUL IN DISCRIMINATING Oh vs Td structures.

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 Magnetic properties of Lanthanides
➢ The f electrons in lanthanides are buried in the (n-2) shell.
➢ Thus 4f orbitals are normally unaffected by the surrounding ligands.
➢ Magnetic moments of Ln3+ ions are generally well described from the coupling of
spin and orbital angular momenta ~ Russel-Saunders coupling to give J vector.
➢ Spin-Orbit coupling constants are large (approximately 1000 cm-1).
➢ Ligand field effects are very small (approximately 100 cm-1).
- Only ground J-state is populated.
- Spin-orbit coupling >> ligand field splitting.

Magnetism is essentially independent of the environment (by approximation).

 e.g. Pr3+, 4f2
(2S+1)L
j
Ml +3 +2 +1 0 -1 -2 -3

2S+1 = 3; L = 5 3H

J = L+S……..L-S = 6, 5, 4
3H
4

μ = gJ√J(J+1)
μ = 4/5 √20 = 3.6
μobs = 3.5 Experiments 3.4 to 3.6 BM
➢ This formula fits well with experimental magnetic moments for all but SmIII and
EuIII ions.
➢ Moments of these ions are altered from the formula due to temperature
dependent population of low lying excited J-states

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 Magnetic susceptibility of some Fe2+
octahedral complexes has sharp decrease, why?
 Spin Cross-over: Vibrational susceptibility

M-L bond distance increases, the compound becomes HS

M-L bond distance decreases, the compound becomes LS
 Low-spin-High-spin transition
-Configurations d4-7 in Octahedral has either LS or HS ground state.
(determined by  and mean spin paring energy P).

- >>P --------> LS and if <<P --------> HS

-However when  <<or >> P not true, a LS  HS transition can occur.

But often | -P|~kT.

eg

d6 high spin Fe(II) d t2g

xz dyz dxy dxz dyz dxy

-Spin transition corresponds to an intraionic electron transfer.

- The occupancy in eg orbitals in the HS state cause elongation of M-L bonds.

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 Spin-Crossover example Fe(II)-d6 ion:
-First example of spin-crossover .

HS
2.22
2.20
1.98 2.08
1.99
1.94

LS

-A abrupt change at ~176 K from S=0 to S=2.

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 From basic science to real time applications: Story on HS-LS
complexes

A Fe(II) HS-LS compound: Colour change

Room Temperature
3

pink

O. Kahn, C. Jay and ICMC Bordeaux

 Application of Spin-Crossover complexes
Display device
LS-HS transition (Spin
crossover) tuneable with light
(or Temperature or Pressure):
Applications

Compound in Display
Low spin state
(Thin Layer)