Topics References

* R. S. Drago, Physical Methods for Chemists, 2nd ed., Chapter 11.

(1) Introduction, definitions, Curie Law
* O. Kahn, Molecular Magnetism
(2) Van Vleck Equation and saturation magnetisation
* J. S. Miller, M. Drillon (eds), Molecules to Materials, vols 1-3
(3) Spin-orbit coupling and zero-field splitting
* C. J. O'Connor, Prog. Inorg. Chem. S. J. Lippard (ed), 1982, 29, 203.
(4) Intermediate spin, spin admixed and spin crossover systems
* J. S. Miller and A. J. Epstein, Angew. Chem. Int. Ed., 1994, 33, 385
(5) Mechanisms of magnetic exchange interactions
* K. S. Murray, Adv. Inorg. Chem. 1995, 43, 261.
(6 & 7) Quntatitative approach to magnetic exchange interactions
* P. S. Gütlich, Y. Garcia, H. A. Goodwin, Chem. Soc. Rev. 2000, 29, 419.
(8) Single-molecule magnets [spin-crossover complexes]

(9) Extended magnetic systems * D. Gatteschi, R. Sessoli, Angew. Chem. Int. Ed. 2003, 42, 268
[single-molecule magnets]
(10) Molecule-based magnets
* M. Verdaguer, Polyhedron, 2001, 20, 1115.
L1, 1 [molecule-based magnets] L1, 2

Introduction to Magnetism Interaction with Magnetic Field

- Ancient Greeks and Chinese knew about "lodestone"
magnetic induction B = H0 + 4πM magnetisation
- Columbus used a magnetic compass when crossing the Atlantic
applied homogeneous field
- Maxwell (1831-1879) established the relationship between
electricity and magnetism
B 4πM
- Magnets used in: electric motors, generators, switches, =1+
sensors, magnetic data storage, televisions, particle H0 H0
accelerators, MRI instruments, medical implants, loudspeakers,
B
microphones and to stick things to the fridge κ = M / H0 = volume magnetic susceptibility

- Responsible for navigation in biological systems: bacteria, H0 χM = κMr / ρ = molar magnetic susceptibility
migratory birds etc (cm3mol-1)
- see http://www.newi.ac.uk/BUCKLEYC/magnet.htm
L1, 3 L1, 4

© School of Chemistry 2005 1

 Behaviour in a Field Gradient Diamagnetism

Diamagnet interaction between e pairs and H0 generates a local

field opposing H0
moves out of
⇒ M, χ < 0
field to lower
energy

M, χ < 0 H0
induces e circulation
induces opposing field
M = -∂E / ∂H (Lenz's Law)

increasing field H0
strength
L1, 5 L1, 6

Behaviour in a Field Gradient Paramagnetism

arises from the interaction between H0 and the
Diamagnet Paramagnet magnetic field of the unpaired e’s associated with their
spin and orbital angular momenta
moves out of moves in to
field to lower field to lower arises principally from the spin angular momentum
energy energy (spin about an internal axis)
M, χ < 0 M, χ > 0 spin angular momentum quantum number: s = 1/2
z-component of spin angular momentum: sz = msh/2π,
ms = ± 1/2
spin magnetic moment: µ = -msgβ
M = -∂E / ∂H
spin angular momentum vector
increasing field
strength
L1, 7 spin magnetic moment vector L1, 8

© School of Chemistry 2005 2

 Experimental Susceptibility Zeeman Splitting
Isolated S = 1/2 system with no orbital contribution
│χpara │ >> │ χdia │
Hamiltonian for interaction of µ with H0: Ĥ = gβH0Ŝ
N2 χM = -12 x 10-6 cm3mol-1 diamagnetic Energies (eigenvalues) given by: E = MsgβH0
O2 χM = 3450 x 10-6 cm3mol-1 paramagnetic
H0 direction Ms = + 1/2
µ
All substances have a diamagnetic component to the
susceptibity, can be estimated by summing the atom Zeeman splitting
Ms = ± 1/2 ∆E = gβH0
susceptibilities – Pascal's Constants (see handout)
µ
χobs = χdia + χ Ms = - 1/2

L1, 9
increasing H0 L1, 10

Derivation of M and χM Derivation of M and χM

µnNn N = Avagadro's number,
H0 direction Ms = + 1/2 M=N∑
Nt Nn = no. of molecules in En,
µ Ms
Nt = total no. of molecules

Ms = ± 1/2 ∑ µ exp(-E /kT)

n n

∴M = N Ms

µ ∑ exp(-E /kT)
Ms
n

Ms = - 1/2
remember µn = -Msgβ, En = MsgβH0, in this case M= ± 1/2
M and χM (≡ M/H0) depend on the relative populations of ⎛ gβ H0 ⎞ gβ ⎛ - gβH0 ⎞
these two states ∑ gβ
2
exp⎜
⎝ 2kT ⎠
⎟ - 2 exp⎜
⎝ 2kT ⎠
⎟
∴M = N Ms

⎛ gβ H0 ⎞ ⎛ - gβ H0 ⎞
µn = magnetic moment for energy level En ∑ exp⎜
⎝ 2kT ⎠
⎟ + exp⎜
⎝ 2kT ⎠
⎟
⇒ calculate M by summing µn of each En weighted by Ms

the Boltzmann population

L1, 11 Ms= -1/2 Ms = + 1/2 terms L1, 12

© School of Chemistry 2005 3

 Derivation of M and χM Curie Law
⎛ g β H0 ⎞ ⎛ - gβ H0 ⎞
Ngβ ∑
exp⎜ ⎟ - exp⎜ ⎟
⎝ 2kT ⎠ ⎝ 2kT ⎠ Ng2 β 2
∴M = Ms
In general χM = S(S + 1)
2 ⎛ g β H0 ⎞ ⎛ - gβ H0 ⎞ 3kT
∑
Ms
exp⎜
⎝ 2kT ⎠
⎟ + exp⎜
⎝ 2kT ⎠
⎟

gβH0 ⎛ ± g β H0 ⎞ gβH0
since << 1 and exp⎜ ⎟ ≈ 1±
2 ⎝ 2kT ⎠ 2kT
χ χ χT

Ng β H0
2 2
∴M =
4kT 1/T T T

M Ng2 β 2 C Curie Law

∴ χM = = = S(S + 1) 3
H0 4kT T (for S = 1/2 system) approximation χMT ≈ cm mol−1K
2
L1, 13 L1, 14

Curie Law Curie Law

1.2
for S=1 χ MT = = 1 cm3mol −1K
2 7
4
S = 1/2, 1, 3/2, 2, 5/2 S = 1/2, 1, 3/2, 2, 5/2
6
2.3
χMT (cm3mol-1K)

χMT (cm3mol-1K)

S=2 χ MT = = 3 cm3mol −1K 3

5
2 4
2 3

2
1
1

χ χT 0
0 50 100 150 200 250 300
0
0 50 100 150 200 250 300
T (K) T (K)

1/T T

L1, 15 L1, 16

© School of Chemistry 2005 4

 Curie-Weiss Law Effective Magnetic Moment
"convenient" (old-fashioned) parameter
1/2
χ ⎛ 3k ⎞
µeff = ⎜⎜ ⎟ ( χ MT)1/2 = 8χ MT = 2.83 χ MT
2 ⎟
⎝ Nβ ⎠

1/T Ng2 β 2
since χM = S(S + 1)
3kT
C
χM = (µeff)2 = g2S(S + 1)
(T + θ )

g = 2 if "spin-only" ie no orbital contribution

θ= Curie-Weiss constant
commonly caused by weak intermolecular interactions µeff = 2 S(S + 1) = n(n + 2) B.M.
L1, 17 L1, 18

Paramagnetism Orbital Contribution

arises from the interaction between H0 and the In a free ion the five d orbs are degenerate and some
magnetic field of the unpaired e’s associated with their can be transformed into others by rotations
z z
spin and orbital angular momenta
90 deg
orbital angular momentum y y
H0 along z induces e
rotn about z
(orbital motion (circulation of charge) about the nucleus) circulation
orbital angular momentum quantum number: L dyz dxz
y y
⇒ orbital angular
momentum about z
µeff = L(L + 1) + 4S(S + 1) 45 deg
x (L ≠ 0)
x
rotn about z

L1, 19 dxy dx2-y2 L1, 20

© School of Chemistry 2005 5

 Orbital Contribution Quenching of Orbital Contribution
Magnetic Moment of first row TMs In an Oh (or Td) ligand field the degeneracy of the d orbs is
config free ion µs+o µs µeff obs at
removed, preventing some of the orbital transfers
3dn, n = ground = [L(L+1) +4S(S+1)]1/2 = [4S(S+1)]1/2 300 K (eg dxy → dx2-y2)
term B.M. B.M.
1 2D
3/2 3.00 1.73 1.7 – 1.8 ⇒ some of the orbital contribution is "quenched"
2 3F
2 4.47 2.83 2.8 – 2.9
3 4F
3/2 5.20 3.87 3.7 – 3.9 Leff = 0 for A and E states
4 5D
0 5.48 4.90 4.8 – 5.0 Leff = 1 for T states
5 6S
5/2 5.92 5.92 5.8 – 6.0
6 5D
4 5.48 4.90 5.1 – 5.7 - orbital contribution only observed for T states
7 4F
9/2 5.20 3.87 4.3 – 5.2 - in less symmetrical ligand fields even more quenching
8 3F
4 4.47 2.83 2.9 – 3.9 is observed
9 2D
5/2 3.00 1.73 1.7 – 2.2 - lanthanide f orbitals are degenerate (even in presence
10 1S
0 0.00 0.00 0 of ligands) and display significant orbital contribution
L1, 21 L1, 22

Example: NiII (d8)

Free ion (3F4) Oh Td

E state T state
S = 1, L = 3 Leff = 0 Leff = 1

µs+o = [L(L+1) +4S(S+1)]1/2

4.47 2.83 4.12 B.M.

µexp = 2.9 – 3.9 B.M.

L1, 23

© School of Chemistry 2005 6

 Topics Fundamental Equations in Molecular Magnetism
(1) Introduction, definitions, Curie Law Macroscopic magnetisation: M = -∂E / ∂H
(2) Van Vleck Equation and saturation magnetisation
En = energy of state n
(3) Spin-orbit coupling and zero-field splitting
Microscopic magnetisation: µn = -∂En / ∂H
(4) Intermediate spin, spin admixed and spin crossover systems

(5) Mechanisms of magnetic exchange interactions to obtain M, must sum the µn's weighted according to
their Boltzmann populations
(6 & 7) Quantitative approach to magnetic exchange interactions
⎛ - En ⎞
(8) Single-molecule magnets ∑ (-δE /δH) exp⎜⎝ kT ⎟⎠
n

(9) Extended magnetic systems

M=N n
⎛ - En ⎞
∑ exp⎜⎝ kT ⎟⎠
(10) Molecule-based magnets n

L2, 1 L2, 2

Van Vleck Equation Van Vleck Equation

µn = -∂En / ∂H
approximation ⇒ En can be expressed as a power series in H0:
= -En(1) - 2En(2)H0 (differentiate eqn above)
En = En(0) + En(1)H0 + En(2)H02 + …
to obtain M (and χM) must sum the µn's weighted
En(0) = energy of state n when H0 = 0 according to their Boltzmann populations

En(1) = 1st order Zeeman coefficient

⎛ -E ⎞
(measure of change in energy of state n due to ∑ (-E − 2En H0) exp⎜ n ⎟
(1) (2)
n
interaction with H0) M=N n ⎝ kT ⎠
⎛ - En ⎞
En(2) = 2nd order Zeeman coefficient ∑n exp⎜⎝ kT ⎟⎠
(measure of change in energy of state n due to
field-induced interaction of state n with higher
energy states)
L2, 3 L2, 4

© School of Chemistry 2005 1

 Van Vleck Equation Van Vleck Equation…Case A
In H0 = 0 there is only one degenerate energy level
after several approximations and rearrangement (see Kahn): eg previous S = 1/2 state, Ms = ±1/2

2 E En(0) = 0 (by convention)

(1)
⎛ -E ⎞
(0)
En
∑( − 2En ) exp⎜⎜ n ⎟⎟
(2)

kT ⎝ kT ⎠ ±1/2 En(1) = Msgβ

χM = N n
En(0) = 0
⎛ - En ⎞
(0)

∑n exp⎜⎜ kT ⎟⎟ En(2) = 0 (no excited states)

⎝ ⎠
⎛E ⎞
(1) 2

general equation that can be applied to many situations ∑ ⎜⎜ n

kT ⎟
⎟ exp(0)
(only valid for moderate H when M vs H plot is linear)
χM = N
n
⎝ ⎠
∑ exp(0)
n
L2, 5 L2, 6

Van Vleck Equation…Case A Van Vleck Equation…Case A'

⎛E ⎞ (1) 2
similarly for S = 1 state, Ms = ±1, 0
∑ ⎜⎜ n ⎟
kT ⎟ ⎛ En(1)2 ⎞
n
⎝ ⎠
χM = N
∑1 ∑ ⎜⎜ ⎟
⎟
n χM = N
n ⎝ kT ⎠
∑1
(1/2gβ )2 ( −1/2gβ )2 n
+
χ M = N kT kT N ⎡ (1gβ )2 + ( −1gβ )2 + (0gβ )2 ⎤
χM =
1+ 1 kT ⎢⎣ 1 + 1+ 1 ⎥
⎦
Ng2 β 2
χM = Curie Law for S = 1/2
4kT 2Ng2 β 2
χM = Curie Law for S = 1
3kT

L2, 7 L2, 8

© School of Chemistry 2005 2

 Van Vleck Equation…Case A' Van Vleck Equation…Case A'
The Curie Law is approximately obeyed by some systems
S Cobs Ccalc

KCr(SO4)2·12H2O KCr(SO4)2·12H2O 3/2 1.84 1.88

4
(NH4)2Mn(SO4)2·6H2O 5/2 4.38 4.38
x 10
10 (NH4)Fe(SO4)2·12H2O 5/2 4.39 4.38
8 Gd2(SO4)3·8H2O 7/2 7.80 7.87
6
1/χ

4
Ng2 β 2 S(S + 1)
C= S(S + 1) ≈
2 3k 2
0
0 50 100 150 200 250 300
T (K) However, there are NO systems that have just one
energy level. Thus, situation A is NEVER valid exactly.
L2, 9 L2, 10

Van Vleck Equation…Case B Van Vleck Equation…Case B

S = 0 ground state and degenerate excited states >> =0 =1 =0
kT above g.s.
⎡ ⎛ (1)2 ⎞ ⎛ E (1)2 ⎞ ⎛ -E ⎞⎤
(0)

⎢ ⎜ Eni − 2Eni(2) ⎟ exp⎛⎜ - Eni ⎞⎟ + ∑ ⎜ nj − 2Enj(2) ⎟ exp⎜ nj ⎟ ⎥

(0)

E ⎢ ⎜ kT ⎟ ⎜ kT ⎟ ⎜ kT ⎟ ⎜ kT ⎟⎥
Eni(0) = 0 Enj(0) >> kT ⎝ ⎠ ⎝ ⎠ n ⎝ ⎠ ⎝ ⎠
χM = N⎢ ⎥
Enj(0) j ⎢ ⎛ ⎞
(0)
⎛ - Eni ⎞ - E ⎥
(0)

⎢ exp⎜⎜ ⎟ + ∑ exp⎜
⎟ ⎜ nj
⎟
⎟ ⎥
Eni(1) = 0 (Ms=0) Enj(1) ≠ 0 ⎝ kT ⎠ n ⎝ kT ⎠
⎢ ⎥
S=0 ⎣ ⎦
Eni(0) = 0 i
Eni(2) ≠ 0 Enj(2) ≠ 0
=1 =0

⎛ − Enj ⎞ χM = −2NEni
(2)
(0)
Eni(2) < 0 and constant, depending on Eni(0) – Enj(0)
exp⎜ ⎟=0
⎝ kT ⎠ χM > 0, constant, independent of T
χ M = Nα
= "temperature independent paramagnetism" (TIP)
L2, 11 L2, 12

© School of Chemistry 2005 3

 Van Vleck Equation…Case C Van Vleck Equation…Case C
S ≠ 0 ground state and degenerate excited states >> deviation from Curie law at high T
kT above g.s.

This is simply the sum of situations A and B: 1/χ χ

Ng2 β 2
χM = S(S + 1) + Nα TIP
3kT
T T

Nα (TIP) is small, so Curie Law term dominates

except at high T - TIP can be estimated by finding the value that makes
the experimental line straight at high T.

L2, 13 L2, 14

Temperature Independent Paramagnetism Van Vleck Equation…Case D

S ≠ 0 ground state and thermally accessible
- size of TIP depends on the energy gap between the degenerate excited states.
ground and excited states
E
⎛ − Eni ⎞
(0)

- typically TIP ≈ 100 x 10-6 cm3mol-1 Eni(0) = 0 ∴ exp⎜⎜ ⎟⎟ = 1

Enk (0) k ⎝ kT ⎠

- is the origin of small paramagnetism that is seen in

diamagnetic compounds eg MnO4-, CrO42- Enj(0) j - no other simplifications possible
- expect complicated T dependence of χ
- consider case by case (see later)
Eni(0) = 0 i

L2, 15 L2, 16

© School of Chemistry 2005 4

 Magnetisation Magnetisation
The Van Vleck equation (and Curie Law) are only valid This gives (see Kahn)
when H/kT is sufficiently small where M is linear in H.
(at 2 K typically want H < 10 kG (1 T)) M = NgβSBS(y) y =gβSH/kT

When H/kT becomes large, M must be calculated from Bs is the Brillouin function

2S + 1 ⎛ 2S + 1 ⎞ 1 ⎛ 1 ⎞
⎛ - En ⎞ BS (y) = coth⎜ y⎟ − coth⎜ y⎟
∑ (-δE /δH) exp⎜⎝ kT ⎟⎠
n 2S ⎝ 2S ⎠ 2S ⎝ 2S ⎠
χM = N n
L2 p1
⎛ - En ⎞
∑ exp⎜⎝ kT ⎟⎠
n
When H/kT → ∞, Bs(y) → 1, M → Msat, M/Nβ → gS

Saturation magnetisation:

Msat = NgβS
L2, 17 L2, 18

Saturation Magnetisation Saturation Magnetisation

Msat = NgβS H0 direction Ms = + 1/2
g = 2.0
5 S = 5/2
Ms = ± 1/2
4 S=2

S = 3/2 Ms = - 1/2
M/Nβ

S=1
2 H0 increasing

S = 1/2
1
When H0 is very large, only Ms = -S (eg Ms = -1/2) is
0 populated
0 1 2

H/T (TK )
-1

L2, 19 L2, 20

© School of Chemistry 2005 5

 Magnetic Field Strength
* Earth's magnetic field at surface 0.1 G

* Permanent bar magnet at 10 cm 100 G

* Superconducting magnets
60 MHz NMR 10 kG (1 T)
400 MHz NMR 100 kG (10 T)
SQUID 70 kG (7 T)

* Hybrid magnets up to 30 T (steady)

up to 100 T (pulsed)

* Cosmic objects (neutron stars) 104 – 108 T

L2, 21

© School of Chemistry 2005 6

 Topics Paramagnetism
(1) Introduction, definitions, Curie Law
arises from the interaction between H0 and the
(2) Van Vleck Equation and saturation magnetisation magnetic field of the unpaired e’s associated with their
spin and orbital angular momenta
(3) Spin-orbit coupling and zero-field splitting

(4) Intermediate spin, spin admixed and spin crossover systems

however spin and orbital angular momentum can couple
(5) Mechanisms of magnetic exchange interactions ⇒ total angular momentum quantum number: J
(1st order spin-orbit coupling)
(6 & 7) Quantitative approach to magnetic exchange interactions

(8) Single-molecule magnets

J takes values from │L + S│ to │L - S│
(9) Extended magnetic systems
MJ = MS + ML
(10) Molecule-based magnets
L3, 1 L3, 2

Spin-Orbit Coupling Spin-Orbit Coupling

Ng2 β 2 eg Ce3+
µeff = g J(J + 1) χM = J(J + 1)
3kT
f1, S = 1/2, L = 3, ground term = 2F

Landé g factor: g ≠ 2 when L ≠ 0 J = 7/2, 5/2

2S+1L
⇒ 2F7/2, 2F5/2 J

3 S(S + 1) − L(L + 1)
g= +
2 2J(J + 1) for shells < half filled, min J is gs
for shells > half filled, max J is gs
for half-filled shells, L = 0 and no spin-orbit coupling
when L = 0, J = S and g = 2

L3, 3 L3, 4

© School of Chemistry 2005 1

 Spin-Orbit Coupling Spin-Orbit Coupling in Rare Earths
Ion Config, Term g µeff(calc) µeff(obs)
eg Ce3+ S = 1/2, L = 3, J = 5/2 4fn, n= =g[J(J+1)]1/2 B.M.
Ce3+ 1 2F
5/2 6/7 2.54 2.4
4F
7/2 Pr3+ 2 3H
4 4/5 3.58 3.5
splitting between J
Nd3+ 3 4I 8/11 3.62 3.5
4F & J+1 = λ(J+1), 9/2

λ is the spin-orbit Pm3+ 4 5I

4 3/5 2.68
coupling constant Sm3+ 5 6H
5/2 2/7 0.84 1.5
4F
5/2 Eu3+ 6 7F
0 3/2 0 3.4
Gd3+ 7 8S
7/2 2 7.94 8.0
Tb3+ 8 7F
6 3/2 9.72 9.5
3 (1/2 ⋅ 3/2) − (3 ⋅ 4) 6 Dy3+ 9 6H 4/3 10.63
g= + = 15/2
2 2 ⋅ 5/2 ⋅ 7/2 7 Ho3+ 10 5I
8 5/4 10.60 10.4
Er3+ 11 4I
15/2 6/5 9.59 9.5
Tm3+ 12 3H 7/6 7.57 7.3
µeff = 6/7 5/2 ⋅ 7/2 = 2.54 B.M. Yb3+ 13 2F
6
8/7 4.54 4.5
L3, 5 7/2 L3, 6

Spin-Orbit Coupling in 3d Metals Spin-Orbit Coupling in d-block Metals

T states of Oh and Td symmetry:
config free ion µs µs+o µso µeff obs 1st order orbital contribution and 1st order spin-orbit coupling
3dn, n = ground = [4S(S+1)]1/2 = [L(L+1)+4S(S+1)]1/2 = g[J(J+1)]1/2 at 300 K
term ⇒ µeff(obs) deviates significantly from µeff(spin only)
B.M. B.M. B.M.
1 2D
3/2 1.73 3.00 1.55 1.7 – 1.8
2 3F
2 2.83 4.47 1.63 2.8 – 2.9 A and E states of Oh and Td symmetry:
3 4F
3/2 3.87 5.20 0.77 3.7 – 3.9 no 1st order orbital contribution
4 5D
0 4.90 5.48 0 4.8 – 5.0 BUT 2nd order spin-orbit coupling , where empty excited
5 6S
5/2 5.92 5.92 5.92 5.8 – 6.0 states with orbital angular momentum are admixed into the
6 5D
4 4.90 5.48 6.70 5.1 – 5.7 ground state via spin-orbit coupling
7 ⇒ µeff(obs) deviates slightly from µeff(spin only)
4F 3.87 5.20 6.63 4.3 – 5.2
9/2
8 3F
4 2.83 4.47 5.59 2.9 – 3.9
9 2D
5/2 1.73 3.00 3.55 1.7 – 2.2
10 1S
0 0.00 0.00 0.00 0

L3, 7 L3, 8

© School of Chemistry 2005 2

 Spin-Orbit Coupling Zero-Field Splitting
the removal of the degeneracy of the Zeeman
- d metals: orbital contribution often quenched
components (Ms states) of the ground state in the
∴ spin-orbit coupling often not important
absence of H0 (for S ≥ 1)
- f metals: f orbitals degenerate because they are eg for S = 1 Ms = ±1
unaffected by ligand field
∴ orbital motion not quenched Ms = 0, ±1
∴ spin-orbit coupling is important
Ms = 0
- gives rise to deviations from ge=2.002 and
anisotropy of the g-factor (gx ≠ gy ≠ gz)
arises from spin-orbit coupling of the ground state with
- important contribution to zero-field splitting empty excited states and a lowering of the symmetry
around Mn+ (induced by ligand field)
L3, 9 L3, 10

Consider Cr3+ in a ML6 (Oh) Complex Consider Cr3+ in a ML6 (Oh) Complex

L Curie Law (spin only formula) applies

L L
CrIII
L L
Ng2 β 2
L χ MT = S(S + 1)
3k

3 5
4A, S = 3/2 ⋅
= 2 2 = 1.88 cm3mol −1K
orbital contribution quenched 2

Ms = ±3/2, ±1/2 all degenerate

L3, 11 L3, 12

© School of Chemistry 2005 3

 Small Axial Distortion eg ML4X2 (D4h) Cr3+ Complex Small Axial Distortion eg ML4X2 (D4h) Cr3+ Complex

X E
±3/2 Eni(0) = 0 Enj(0) = 2D
±3/2 L L 2D j
CrIII
±1/2, ±3/2 L L Eni(1) = Msgβ Enj(1) = Msgβ
2D X ±1/2
z-axis 0 i
Eni(2) = 0 Enj(2) = 0
±1/2

D = axial ZFS parameter Enij(2) = 0 because 1st excited state is far above in energy (∆o)
H0 = 0
(∆o ≈ 10 000 – 20 000 cm-1)

How do we determine χM? ∆o

…use the Van Vleck Equation (Case D)

L3, 13 gs es L3, 14

Small Axial Distortion eg ML4X2 (D4h) Cr3+ Complex Small Axial Distortion eg ML4X2 (D4h) Cr3+ Complex

apply H0 parallel to molecular z-axis Van Vleck Equation:

(1) 2 (0)
En -E
∑( − 2En ) exp( n )
(2)

+3/2
kT kT
±3/2 χMΙΙ = N n
(0)
- En
±1/2, ±3/2 ∑n exp( kT )
-3/2
i (MS = ±1/2) j (MS = ±3/2)
±1/2 +1/2

-1/2
1 3 - 2D
N 2( 2 gβ ) exp(0) + 2( 2 gβ ) exp( kT )
2 2

χMΙΙ =
H0 = 0 H0 inc kT - 2D
2exp(0) + 2exp( )
kT
L3, 15 L3, 16

© School of Chemistry 2005 4

 Small Axial Distortion eg ML6X2 (D4h) Cr3+ Complex Small Axial Distortion eg ML4X2 (D4h) Cr3+ Complex

⎡ - 2D ⎤ Thus at low T, χMT will drop to that expected for a

1 + 9exp( )
Ng2 β 2 ⎢ kT ⎥ S = 1/2 system
χ =
ΙΙ
M ⎢ ⎥
4kT ⎢ 1 + exp( - 2D ) ⎥
⎣ kT ⎦ χΜ‫װ‬T

1.9

When 2D → 0 or T → ∞ When 2D → ∞ or T → 0
0.4
5Ng2 β 2 Ng2 β 2
χ MΙΙ = χ =
ΙΙ
M
T
4kT 4kT

Curie Law for S = 3/2 Curie Law for S = 1/2 2D for Cr3+ ≈ 0.1 cm-1
(χMT = 1.88 cm3mol-1K) (χMT = 0.38 cm3mol-1K)
L3, 17 L3, 18

Effect of ZFS on Magnetic Susceptibility Effect of ZFS on Magnetic Susceptibility

For S = integer and significant D or very low T
⇒ χΜ‫װ‬T → 0 as if diamagnetic - the susceptibility is anisotropic

±1 - χM‫ װ‬is for H0 applied along z axis

eg for S = 1
0, ±1 - mathematics for χM┴, with H0 applied along x or y
axes is a little more complex
0
χΜ‫װ‬T - for a powder, the "powder average" is:

1 χMΙΙ + 2 χM⊥
χM =
3
0

T L3, 19 L3, 20

© School of Chemistry 2005 5

 Axial ZFS Parameter D General Method for ZFS Energies
E(Ms) is the energy of a particular Ms state
Typical D values for 1st row TMs: 0 – 5 cm-1
E(Ms) = (Ms)2D
D can also be negative ⇒ larger Ms value of lower energy
S=2 S = 5/2
eg for S = 1 ±5/2 (25D/4) 4D
±2 4D
±1 0
4D
3D
D D
±3/2 (9D/4) 2D
±1 ±1 D
0 2D
D
0 0 ±1/2 (D/4) 0
D +ve D -ve
L3, 21 Ms E(Ms) Ms E(Ms) L3, 22

ZFS of S ≥ 1 States Examples

S χM‫װ‬ NiII: D = 5 cm-1 (g = 2.0)

2e − x
1 C⋅ perpendicular
1+ 2e −x Ng2 β 2 0.4
parallel
C= average 1.0
kT
χMT (cm3mol-1K)
χM (cm3mol-1)

0.3
1 + 9e −2x
3/2 C⋅
4(1+ e −2x ) D 0.2
x= 0.5
−4x
kT
2e + 8e
-x
0.1 perpendicular
2 C⋅ parallel
1+ 2e −x + 2e−4x average
0.0 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
1 + 9e -2x + 25e −6x T (K) T (K)
5/2 C⋅
4(1+ e−2x + e−6x )

L3, 23 L3, 24

© School of Chemistry 2005 6

 Examples Axial ZFS Parameter D
high spin MnIII: D = -5 cm-1 (g = 2.0)
λ⎡ gx + gy ⎤
D= gz −
7
2 ⎢⎣ 2 ⎥⎦
6
perpendicular perpendicular
parallel 6 parallel
5
average average
λ = spin orbit coupling constant
χMT (cm3mol-1K)

5
χM (cm3mol-1)

4
4
3
3
2
ZFS ⇒ deviation from the Curie Law associated
2
with magnetic anisotropy (χM‫ ≠ װ‬χM┴)
1 1

0
0 50 100 150 200 250 300
0 D < 0 "easy-axis" (Ising) magnetic anisotropy
0 50 100 150 200 250 300
T (K) T (K)
D > 0 "hard-axis" or "easy plane" magnetic
anisotropy
L3, 25 L3, 26

© School of Chemistry 2005 7

 Magnetic Interactions in Polynuclear Molecules [Cu2(O2CMe)4(H2O)2]
Cu(SO4) obeys the Curie Law

"Cu(O2CMe)2·H2O" does not obey the Curie Law

antiferromagnetic coupling between Cu2+ centres

L5, 1 L5, 2

Magnetic Exchange Interactions Ferromagnetic and Antiferromagnetic Interactions

Definitions:
Exchange interactions can be:
- magnetic orbital: orbital containing an unpaired e
- ferromagnetic: parallel arrangement of "spins", J > 0
- exchange interactions: interaction between different
metal centres with unpaired e's
M1 M2
- coupling constant (J): measure of the magnitude of
the exchange interaction
- antiferromagnetic: antiparallel arrangement of "spins", J < 0
Heisenberg (isotropic) Hamiltonian describes the
interaction:
M1 M2
Ĥ = -2JŜA·ŜB
L5, 3 L5, 4

© School of Chemistry, University of Melbourne 2005 1

 Ferromagnetic and Antiferromagnetic Interactions Ferromagnetic and Antiferromagnetic Interactions

For two coupled S = 1/2 centres For two coupled S = 1/2 centres

ferromagnetic (J > 0) antiferromagnetic (J < 0)

1.2
J=0
-1
J = -100 cm 1.0
-1
J = 100 cm
E E

χMT (cm3mol-1K)
0.02 0.8

χM (cm3mol-1)
S=0 S=1
Δ = 2J Δ = −2J 0.6

S=0 0.4
S=1
J=0
0.2 J = -100 cm
-1

-1
J = 100 cm
0.00 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
excited state populated at room temperature T (K) T (K)

L5, 5 L5, 6

Mechanisms of Antiferromagnetic Exchange Interactions Direct Interactions

Consider a strong M-M bond:

Exchange interactions can be:

M M M M
- direct interaction ⇒ direct through space overlap of
magnetic orbitals
2 ML5 fragments with 1 upe each σ bond formation
- superexchange ⇒ magnetic orbitals interact via the eg Mn(CO)5˙ Mn2(CO)10
filled orbitals of bridging ligands (most important)
σ∗
- spin polarisation ⇒ interaction without orbital overlap Δ = large vs kT

∴ all molecules have S = 0 ground state

and M-M bond DIAMAGNETIC
S = 1 excited state (no bond) far above
σ ground state

L5, 7 L5, 8

© School of Chemistry, University of Melbourne 2005 2

 Direct Interactions Direct Interactions
Consider a weak M-M bond: Consider a weak M-M bond:

z
δ∗
δ overlap is weak
E
S=1
Δ = −2J
δ
S=0
dx2-y2 dx2-y2

δ∗ δ∗

Δ = small If Δ not large (< 10 000 cm-1), thermal energy sufficient

vs kT
to populate excited state
∴ sample will show magnetic behaviour associated
δ δ
with S = 1 state PARAMAGNETIC
S=0 S=1
ground state excited state L5, 9 L5, 10

Direct Interactions in [M2O2L6]n+ Mechanisms of Magnetic Exchange Interactions

O d1
L L L Exchange interactions can be:
L L y
M M M
L L x L L L - direct interaction ⇒ direct through space overlap of
magnetic orbitals

dxy - superexchange ⇒ magnetic orbitals interact via the

filled orbitals of bridging ligands (most important)
M = VIV (3d)
V…V dist ≈ 3 Å, weak orbital overlap, no V-V bond - spin polarisation ⇒ interaction without orbital overlap
S = 0 g.s. and S = 1 e.s. populated at RT PARAMAGNETIC

M = MoV (4d)
Mo…Mo dist ≈ 2.7 Å, larger 4d orbitals overlap, single Mo-Mo bond
only S = 0 g.s. populated at RT DIAMAGNETIC
L5, 11 L5, 12

© School of Chemistry, University of Melbourne 2005 3

 Superexchange Interactions Superexchange Interactions
Consider 2 M centres bridged by one L eg O2- to give M2O Consider 2 M centres bridged by one L eg O2- to give M2O

(1) σ-overlap M1 O M2 (1) σ-overlap

z E σ*
ΔΕ
dz2 pz dz2
n

M-O-M σ*
E ΔΕ S=0 S=1
M-O-M n g.s. e.s.

3d metals: ΔE not large vs kT ∴ thermal population of e.s.

….PARAMAGNETIC
M-O-M σ 4d and 5d metals: ΔE large vs kT ∴ no thermal population of e.s.
M1M2 M1-O-M2 O ….DIAMAGNETIC
L5, 13 L5, 14

Superexchange Interactions Superexchange Interactions

Consider 2 M centres bridged by one L eg O2- to give M2O Consider 2 M centres bridged by one L eg O2- to give M2O
M1 O M2
(1) π-overlap (1) π-overlap π*
x E
ΔΕ
z
dxz px dxz n

M-O-M π* S=0 S=1

E ΔΕ
M-O-M n g.s. e.s.

3d metals: ΔE not large vs kT ∴ thermal population of e.s.

….PARAMAGNETIC
M-O-M π 4d and 5d metals: ΔE large vs kT ∴ no thermal population of e.s.
….DIAMAGNETIC
M1M2 M1-O-M2 O L5, 15 L5, 16

© School of Chemistry, University of Melbourne 2005 4

 [Cu2(O2CR)4(H2O)2]…Direct Interaction or Superexchange? [Cu2(O2CR)4(H2O)2]…Direct Interaction or Superexchange?

Cu2+ E
S=1
z Δ = −2J
dx2-y2
O O S=0
magnetic orbital O O
H2O Cu Cu OH2
dxy
O O
O O R=H R = Me
dz2 Cu…Cu = 2.72 Å Cu…Cu = 2.64 Å
-2J = 485 cm-1 -2J = 305 cm-1
dxz, dyz
Also correlation between pka of RCO2H and ΔE
(↑ acidity ⇒ stronger coupling)
antiferromagnetic interaction
direct interaction and superexchange both possible ⇒ SUPEREXCHANGE is the main mechanism
L5, 17 L5, 18

Mechanisms of Magnetic Exchange Interactions Spin Polarisation

If no orbital overlap because wrong symmetry, ionic bonding etc,
can still get AF coupling, eg. ionic MnO
Exchange interactions can be:
Mn O Mn
z
- direct interaction ⇒ direct through space overlap of σ orientation
S = 0 g.s.
magnetic orbitals (S = 1 e.s.)
dz2 pz dz2
OR
- superexchange ⇒ magnetic orbitals interact via the
filled orbitals of bridging ligands (most important) x π orientation
S = 0 g.s.
- spin polarisation ⇒ interaction without orbital overlap z
(S = 1 e.s.)
dxz px dxz
- tendency of ↑ to repel ↑ polarises spin distribution in filled pz orbital
- note: electron distribution is still symmetric, spin (↑ or ↑ ) is polarised
- often the cause of weak intermolecular interactions
L5, 19 L5, 20

© School of Chemistry, University of Melbourne 2005 5

 Ferromagnetic Exchange Ferromagnetic Exchange
Heteronuclear MM' system σ∗
Homonuclear M2 system
σ∗
Δ δ
2Jobs ≈ 2j -2S0(Δ2-δ2)1/2
Δ
σ
JF JAF
σ
S0 = overlap integral

if Δ > P
Δ >> exchange energy if Δ large and δ small, JAF >> JF ⇒ antiferromagnetic exchange
⇒ S = 0 g.s. and antiferromagnetic exchange
if Δ small and δ large, JAF < JF ⇒ ferromagnetic exchange
if Δ gets small
⇒ S = 1 g.s. and ferromagnetic exchange if S0 = 0, JAF < JF ⇒ ferromagnetic exchange
L5, 21 L5, 22

Mechanisms of Ferromagnetic Exchange Interactions Strictly Orthogonal Magnetic Orbitals

dx2-y2 M = CuII (d9)
sq planar
- orthogonal magnetic orbitals (no overlap) O dxy AF, J = -325 cm-1

N O O dz2
- overlap of a magnetic orbital on one metal with an
empty orbital on another CuII M
dxz, dyz

N O O
dx2-y2 M = VIV (d1) [V=O]
sq pyramid
O F, J = 59 cm-1
dz2

dxz, dyz
L5, 23 dxy L5, 24
O. Kahn et al J. Am. Chem. Soc. 1982, 104, 2165

© School of Chemistry, University of Melbourne 2005 6

 Strictly Orthogonal Magnetic Orbitals "Accidentally" Orthogonal Magnetic Orbitals
(CuII)2 CuIIVIV py px
(CuII)2 complex
L y
O O
L
M2 CuII CuII
CuII CuII CuII VIV O M1 θ

θ = 90º L x
O O dx2-y2 dx2-y2
dx2-y2 dx2-y2 dx2-y2 dxy

M1: S0(dx2-y2/px) ≠ 0 S0(dx2-y2/dx2-y2) = 0,

S0 ≠ 0 S0 = 0 M2: S0(dx2-y2/py) ≠ 0 ie magnetic orbitals are orthogonal
AF, J = -325 cm-1 F, J = 59 cm-1 S0(px/py) = 0 ⇒ S = 1 g.s. due to
ferromagnetic interaction

L5, 25 L5, 26

Hydroxo-bridged Cu(II) Dinuclear Complexes

[Cu2(OH)2L2]2+

N H N
O
Cu Φ Cu
O
N H N

correlation: J = -74Φ + 7270

crossover from F to AF at 97.5º

V. H. Crawford et al Inorg. Chem. 15, 1976, 2107. L5, 27

© School of Chemistry, University of Melbourne 2005 7

 Topics Quantitative Approach to Exchange Interactions
(1) Introduction, definitions, Curie Law
For 2 coupled S = 1/2 spins (eg Cu2 dimer)
(2) Van Vleck Equation and saturation magnetisation
Ĥ = -2JŜA·ŜB
(3) Spin-orbit coupling and zero-field splitting

(4) Intermediate spin, spin admixed and spin crossover systems assuming no orbital contribution or ZFS
E
(5) Mechanisms of magnetic exchange interactions
-2J S = 1 (j) Eni(0) = 0 Enj(0) = -2J
(6 & 7) Quantitative approach to magnetic exchange interactions

0 S = 0 (i) Eni(1) = Msgβ Enj(1) = Msgβ

(8) Single-molecule magnets

(9) Extended magnetic systems Eni(2) = 0 Enj(2) = 0

(10) Molecule-based magnets
L6, 1 L6, 2

Quantitative Approach to Exchange Interactions Quantitative Approach to Exchange Interactions

Use Van Vleck…
2 ⎡ ⎛ 2J ⎞ ⎤
(1)
⎛ -E ⎞ exp⎜ ⎟ ⎥
2Ng2 β 2 ⎢
(0)
En
∑( − 2En ) exp⎜⎜ n ⎟⎟ ⎝ kT ⎠ ⎥
(2)

kT χM = ⎢
⎝ kT ⎠ kT ⎢ ⎛ 2J ⎞
χ =N 1+ 3exp⎜ ⎟ ⎥
n

⎛ - En ⎞
(0)
M
⎢⎣ ⎝ kT ⎠ ⎥⎦
∑n exp⎜⎜ kT ⎟⎟
⎝ ⎠
(multiply numerator and denominator by exp(-2J/kT))
i: ST = 0 j: ST = 1 (Ms = ±1, 0)

⎡ ⎤
⎡ 2Ng2 β 2 ⎢ 1 ⎥
⎛ 2g2 β 2 ⎞ ⎛ 2J ⎞ ⎤ χM = ⎢ ⎥
⎢ 0 exp(0) + ⎜⎜ + 0 ⎟⎟exp⎜ ⎟ ⎥ kT ⎢ ⎛ - 2J ⎞ ⎥
⎝ kT ⎠ ⎝ kT ⎠ ⎥ 3 + exp⎜ ⎟⎥
χ M = N⎢ ⎢⎣ ⎝ kT ⎠ ⎦
⎢ ⎛ 2J ⎞ ⎥
⎢ exp(0) + 3exp⎜ ⎟ ⎥
⎣ ⎝ kT ⎠ ⎦ Bleaney-Bowers Equation
L6, 3 L6, 4

© School of Chemistry, University of Melbourne 2005 1

 Topics Extended Magnetic Systems
(1) Introduction, definitions, Curie Law
* atom based
(2) Van Vleck Equation and saturation magnetisation
* spins contained on d or f block metals
(3) Spin-orbit coupling and zero-field splitting

(4) Intermediate spin, spin admixed and spin crossover systems * pure metals, alloys, oxide/sulfide/halide containing
network solids
(5) Mechanisms of magnetic exchange interactions
* typically synthesised by high temperature
(6 & 7) Quantitative approach to magnetic exchange interactions
"metallurgical" means
(8) Single-molecule magnets

(9) Extended magnetic systems

(10) Molecule-based magnets

L9, 1 L9, 2

Magnetism in Extended Systems Curie Paramagnets

Paramagnet Ferromagnet

H=0 H⇑ H=0

M
Antiferromagnet Ferrimagnet
χ χ

1/T T

L9, 3 L9, 4

© School of Chemistry, University of Melbourne 2005 1

 Curie-Weiss Paramagnets Ferromagnets
Tc = θ = Curie temperature (phase transition)

C T < Tc (long range order)

χM = χ
(T + θ )

1/T

θ = Curie-Weiss constant
T > Tc (paramagnetic)
caused by interactions between spins in extended systems
Below TC, χ is not a useful
θ > 0: ferromagnetic interactions parameter as it is field and
θ < 0: antiferromagnetic interactions history dependent. M is
used instead.
L9, 5 L9, 6

Ferromagnets Ferromagnet - Domains

Shows hysteresis due to movement of domain walls Ferromagnetic cooled below TC with H = 0 ⇒ domains
M
MS = saturation magnetisation MS
MR = remanent magnetisation MR ≡
HC = coercive field
virgin curve

HC M

L9, 7 L9, 8

© School of Chemistry, University of Melbourne 2005 2

 Ferromagnets – Hard and Soft Ferromagnets – Hard and Soft

MR, HC big (> 100 G) ⇒ "hard ferromagnet"

M M M
* eg Fe-based alloys (with Al, Co, Cr, …, Nd2Fe14B)
Hard Soft and oxides, CrO2, SmCo5
* "permanent magnets", magnetic recording media
H H H

MR, HC small (< 10 G) ⇒ "soft ferromagnet"

* eg elemental Fe, Fe-based alloys (Ni80Fe20)

* used in electromagnets, magnetic motors, generators,
transformers, ac shielding

L9, 9 L9, 10

Ferromagnets – Examples Antiferromagnets

TN = |θ| = Néel temperature (phase transition)
Material TC (K)
N (long
T <T T<NT(long range
range order)
order)
Co 1388
Fe 1043
Fe2B 1015
Fe3P 716
Cu2MnAl 630
Ni 627
CrO2 393 T > TN (paramagnetic)
MnAs 318
Gd 293
CrBr3 37
GdCl3 2.2

L9, 11 L9, 12

© School of Chemistry, University of Melbourne 2005 3

 Antiferromagnets - Examples Antiferromagnets

* In nature antiferromagnetic coupling is much more

Material TN (K)
common than ferromagnetic coupling
α-Fe2O3 953
* Antiferromagnets find application in "exchange-biased"
LaFeO3 750
materials (read/write heads based on "giant
FeS 613
magnetoresistance"
FeF3 394
FeO 198
* Fewer practical applications for antiferromagnets than
MnO 122
ferromagnets
KFeF3 113
MnF3 45
CoF2 40
VF3 <4

L9, 13 L9, 14

Ferrimagnets Ferrimagnets - Examples

TfN = ferrimagnetic Néel temperature (phase transition)
Material TfN (K)

T < TfN (long range order) 1/χ Fe3O4 858

γ-Fe2O3 856
BaFe12O19 820
Y3Fe5O12 553

Typically metal oxides with spinel or garnet structures

T
T > TfN (paramagnetic) Often structure can be regarded as two independent
Ferrimagnets have sublattices which are antiferromagnetic with respect
antiferromagnetic coupling to one another
but uncompensated spins
⇒ "ferromagnetic-like"
behaviour L9, 15 L9, 16

© School of Chemistry, University of Melbourne 2005 4

 Magnetite – Fe3O4 – A Spinel Ferrimagnets

Below TfN ferrimagnets have a net moment like

FeIIFeIII2O4 ferromagnets
FeIII – tetrahedral (↑)
FeII/FeIII – octahedral (↓) Used in magnetic recording (γ-Fe2O3) and as
permanent magnets in inductance cores (BaFe12O19,
Y3Fe5O12), where a metallic material would show
in each formula unit: large eddy current losses
S = 5/2 ↑
S = 5/2 + 2 ↓
⇒S=2↓

L9, 17 L9, 18

Spin Canting Metamagnets

Layered structure, ferromagnetic interaction within layers

weaker antiferromagnetic interaction between layers

net magnetic moment F

M

AF

antiferromagnetic coupling, but alignment of spins not

exactly antiparallel H
⇒ can lead to weak apparent ferromagnetism
characteristic sigmoidal response

L9, 19 L9, 20

© School of Chemistry, University of Melbourne 2005 5

 Superparamagnets Paramagnets, Superparamagnets and Ferromagnets

Single domain particles (~ 10 nm) of ferro-, ferri-, or M

antiferromagnets
Paramagnet
H

H=0 H→ H=0

M
TB = blocking temperature Super-
paramagnet H
T > TB: The magnetic moment is thermally unstable, easily
T > TB
magnetically saturated but have small/zero H=0 H→ H=0
remanent magnetisation and coercivity
M

T < TB: Display hysteresis and "apparent" ferromagnetic Ferromagnet

H
behaviour
L9, 21 H=0 H→ H=0 L9, 22

Magnets in Biological Systems - Ferritin Ferritin Core

found in animals, Fe stored as

plants and bacteria "ferrihydrite":
5Fe2O3•9H2O
24 subunits arranged
around a central cavity 4-8 nm diameter
where Fe is stored in
mineral form up to 4500 Fe atoms

L9, 23 L9, 24

© School of Chemistry, University of Melbourne 2005 6

 Magnetic Behaviour of Ferritin Ferritin and Hemosiderin
Ferritin: * Fe storage protein
Depends on size and type of ferritin, * soluble
* superparamagnetic, TB ~ 15 - 50 K
generally antiferromagnetic and superparamagnetic * ferrihydrite (5Fe2O3•9H2O), amorphous
with TB ~ 15 - 50 K
Hemosiderin: * Fe storage protein
* insoluble
* superparamagnetic, TB ~ 80 K
* goethite (α-FeOOH), crystalline

hemosiderin deposits
L9, 25 L9, 26

Magnetotactic Bacteria Magnetotactic Bacteria

Bacteria orient and migrate along geomagnetic field lines
some are north-seeking and some are south seeking

Due to the presence of magnetosomes, which are

magnetic mineral particles enclosed in membranes

magnetosomes:
* magnetite (Fe3O4) or greigite (Fe3S4)
* single crystals, 40–100 nm
* arranged in a chain
* single domain magnetic particles with permanent
magnetic domain
* ferrimagnetic at room temperature

L9, 27 L9, 28

© School of Chemistry, University of Melbourne 2005 7

 Magnetosomes
TEM pictures of
Crystal habits of the minerals
magnetosomes

L9, 29

© School of Chemistry, University of Melbourne 2005 8