1.

MOLECULAR MAGNETISM
Introduction

Magnetochemistry is the study of the magnetic properties of materials. By "magnetic

properties" we mean not only whether a material will make a good bar magnet, but whether it
will be attracted or repelled by a magnet.

Magnetism arises from moving charges, such as an electric current in a coil of wire. In a
material which does not have a current present, there are still magnetic interactions. Atoms
are made of charged particles (protons and electrons) which are moving constantly.

The processes which create magnetic fields in an atom are:

 Nuclear spin. Some nuclei, such as a hydrogen atom, have a net spin, which creates
a magnetic field.
 Electron spin. An electron has two intrinsic spin states (similar to a top spinning)
which we call up and down or alpha and beta.
 Electron orbital motion. There is a magnetic field due to the electron moving around
the nucleus.
Each of these magnetic fields interacts with one another and with external magnetic fields.
However, some of these interactions are strong and others are negligible.

Magnetism in solids originates in the magnetic properties of an electron.

Fig. 1: Magnetic fields due to a bar magnet and a circuital current.

Fig. 2: Magnetic fields due to a magnetic moment and a small circular current.

Magnetism

The classical theory of magnetism was well developed before quantum mechanics. Lenz's
Law (~1834), states that: “when a substance is placed within a magnetic field, H, the field
within the substance, B, differs from H by the induced field, 4πI, which is proportional to the
intensity of magnetization, I”.

That is; B = H + 4πI

where B is the magnetic field within the substance, H is the applied magnetic field and I is
the intensity of magnetization.

This can also be written as

B/H = 1 + 4π I/H, or B/H = 1 + 4pκ

where B/H is called the magnetic permeability of the material and k is the magnetic
susceptibility per unit volume, (I/H)

By definition, κ in a vacuum is zero, so that B=H.

Traditionally, magnetism is discussed in terms of susceptibilities which may be defined as

follows:

Volume susceptibility  = I / H

Gram susceptibility, g =  /  (where  = density)

Molar susceptibility, M =  . M.Wt.

It is usually more convenient to measure mass (gram) susceptibility, χ g, which is related to

the volume susceptibility through the density.

M is also defined by the Lande equation, such that

N A 2
M 
3kT
Where NA = Avogadro’s number, μ = magnetic moment, k = Boltzmann constant and T =
temperature. Rearranging this equation gives:

 3kT 
   . M
 NA 

μ is usually referred to as the effective magnetic moment, and by enumerating the constants
the equation becomes
 eff  2.83  M .T

There are two major types of behaviour when a substance is placed in a magnetic field:
If B < H the substance is said to be diamagnetic. It is repelled by the field and  is negative.
Diamagnetism occurs as a result of electrons in closed shells circulating under the influence
of the external magnetic field to generate a local field which is in opposition to the external
field.

If B > H the substance is said to be paramagnetic. It is attracted by the field and  is positive.
Paramagnetism arises from the interaction of the spin and angular momentum of unpaired
electrons with the external field. (If the spins are paired the spin and angular momentum
cancel each other out). Note that paramagnetism is roughly 3 orders of magnitude greater
than diamagnetism – hence, although paramagnetic species will have a diamagnetic
contribution to the magnetic moment due to the core electrons in closed shells, the
magnitude of this effect is relatively small (ca 1 – 5 %).

Types of Magnetism

(1) Diamagnetism
Magnetic property of a material as a result of the circulation of closed (complete) shells of
electrons. The magnetism produced acts in opposition to that of the applied field. This is
characteristic of molecules with no unpaired electrons. A diamagnetic compound has all its
electron spins paired giving a net spin of zero. Diamagnetic compounds are weakly repelled
by a magnet.

(2) Paramagnetism
Magnetic property arising for the unbalanced spin of electrons around the nuclei in
molecules possessing unpaired electrons. A paramagnetic compound will have some
electrons with unpaired spins. Paramagnetic compounds are attracted by a magnet.
Paramagnetism derives from the spin and orbital angular momenta of electrons. This type of
magnetism occurs only in compounds containing unpaired electrons, as the spin and orbital
angular momenta is cancelled out when the electrons exist in pairs. When a magnetic field is
applied the spins tend to orientate themselves in the direction of the field and possess a
positive magnetic susceptibility, i.e. are attracted towards the magnetic field. Paramagnetic
effects are generally much larger than diamagnetic effects. Examples: NO 2, NO (1 unpaired
electron), O2 (2 unpaired electrons), and many transition metal ions which can adopt
alternative spin states depending on the geometry and the ligands, e.g. Ni 2+ square planar
are diamagnetic; tetrahedral are paramagnetic.

Compounds in which the paramagnetic centres are separated by diamagnetic atoms

within the sample are said to be magnetically dilute. Paramagnetic substances always
have the majority of their electrons paired, so they have diamagnetic behaviour as well, but
this is masked by the much larger paramagnetic effect. In such species the magnetic
moment is given by the expression

  4S S  1  LL  1

Where S is the total spin (i.e. the sum of values of m s) and L is the total orbital angular
momentum (ie the sum of the values of ml).
For many compounds the sum of the orbital angular momentum is zero, so we can use the
spin-only formula as a good approximation to the magnetic moment as given by:

 spinonly  4S S  1

This can also be expressed in terms of the number of unpaired electrons, n (since n = 2S)
 spinonly  nn  2 

Normal paramagnetic substances obey the Curie Law

χ = C/T

where C is the Curie constant. Thus a plot of 1/χ versus T should give a straight line of slope
1/C passing through the origin (0K). Many substances give a straight line that intercepts just
a little above 0K and these are said to obey the Curie-Weiss Law:

χ = C/(T+φ) ; where φ is known as the Weiss constant.

The constant C is given by the Langevin expression, which relates the susceptibility to the
magnetic moment:

χm = Nμ2 / 3kT

where N is Avogadro's number, k is the Boltzmann constant and T the absolute temperature.
Rewriting this gives the magnetic moment as

μ=2.828 √ χ m . T

 Diamagnetism and paramagnetism are characteristic of compounds with individual

atoms which do not interact magnetically (e.g. classical complex compounds)
(3) Ferromagnetism
There are, however, many compounds in which the neighbouring magnetic centres can
interact (or couple) with each other, leading to magnetic ordering of the bulk material. In a
ferromagnetic substance the magnetic spins on one molecule prefer to line up parallel to
those on neighbouring molecules. This preference may be sustained over many thousands
of unit cells to create a magnetic domain.

If the magnetic moments all line up in parallel (as shown below) then the species is said to
be ferromagnetic.



In ferromagnetic compounds μeff is generally much greater than μspin-only due to the
cooperative effect of the spins coupling in parallel which reinforces the bulk magnetic
moment. The most common ferromagnetic materials are metals such as iron and cobalt and
their alloys. CrO2 is a rare example of a binary compound which is ferromagnetic at room
temperature.

(4) Anti-ferromagnetism
In an anti-ferromagnetic substance the magnetic spins on one molecule prefer to lie anti-
parallel to those on neighbouring molecules and consequently the susceptibility below the
Néel temperature falls relative to that expected from the Curie law..

If the magnetic moments line up antiparallel with respect to one another (as shown below)
then the substance in said to be antiferromagnetic.



In antiferromagnetic compounds μeff tends to be somewhat less than μ spin-only since the
coupling of the spins into an anti-parallel arrangement results in the individual magnetic
moments cancelling one another out. Antiferromagnetic materials are much more common
than ferromagnetic materials.

Many metal halides and oxides are antiferromagnetic. Examples include:

α-TiCl3 μeff = 1.31 B.M. (μspin-only = 1.73 B.M.)

VCl3 μeff = 2.42 B.M. (μspin-only = 2.83 B.M.)

(5) Ferrimagnetism
In ferrimagnetic substances a net magnetic ordering is observed below the Néel
temperature, because the spins align in an anti-parallel fashion, but since there is more than
one type of magnetic centre in the substance the spins do not cancel out completely. The
sample therefore has a net magnetic susceptibility even at absolute zero.

 Ferromagnetism, anti-ferromagnetism and other types of cooperative magnetism

originate from an intense magnetical interaction between electron spins of many
atoms

Fig. 3:

Transition metal oxides, MO, all have the NaCl structure although at times they are not
simple stoichiometric compounds. In the NaCl structure the octahedral environment around
the metal leads to the e g‒t2g splitting. The non-bonding t2g set point towards the matching
orbitals on the adjacent metal ions and the overlap between the t 2g orbitals is small but
sufficiently significant for a band structure to develop.

If the ordering occurs in such a way that the electron spins on the metals all orientate
preferentially in a parallel fashion, Fig. 3a, ferromagnetism results. If the electron spins on
the metals preferentially align in an anti-parallel fashion, Fig. 3b, anti-ferromagnetism results.
If the interactions which results in these alignments are strong the transition from
ferromagnetic or anti-ferromagnetic behaviour to paramagnetic behaviour occurs at a high
temperature, whereas if they were weak very low temperatures are required for this
transition.

An important mechanism by which the spins of metal ions align in solids in the super
exchange mechanism. The coupling of the magnetic moments arises via a mechanism
known as super-exchange, in which the ligands help to order the spins on the metal centres.
In the metal oxides MO which have the NaCl structures the electrons in the e g orbitals can
interact with the orbital pair in the p orbitals of the oxide to polarise the electron spin on the
adjacent metal ion in an anti-parallel fashion, i.e. leading to an anti-ferromagnetic interaction.
Consequently, the metal oxides MnO, Fe 1-xO, CoO and NiO, which have electrons occupying
the e.g. orbitals exhibit antifeeromagnetic interactions. The corresponding Néel temperatures
are:

MnO (122 K), Fe1-xO (198 K), CoO (293 K) and NiO (523 K). The increasing Néel
temperature across the series reflects the stronger metal-ligand interactions across the
series as the metal ions contract insize.

Ferromagnetic and antiferromagnetic coupling is not restricted to ionic lattice type

compounds, but can also be observed in polymetallic molecular compounds. So simple
dimers and larger clusters can have the magnetic moments from neighbouring metal ions
coupled via bridging ligands giving rise to discrete magnetic molecular entities which exhibit
a degree of magnetic ordering.

Temperature Dependence of Magnetic Susceptibilities

The magnetic moments (and susceptibilities) of paramagnetic materials on the whole show
marked temperature dependence as shown in the idealised plot below.
These two forms of paramagnetism show characteristic variations of the magnetic
susceptibility with temperature.

In the case of ferromagnetism, above the Curie point the material displays "normal"
paramagnetic behavior. Below the Curie point the material displays strong magnetic
properties. Ferromagnetism is commonly found in compounds containing iron and in alloys.

For antiferromagnetism, above the Neel point the material displays "normal" paramagnetic
behavior. Below the Neel point the material displays weak magnetic properties which at
lower and lower temperatures can become essentially diamagnetic. Antiferromagnetism is
more common and is found to occur in transition metal halides and oxides, such as TiCl 3 and
VCl2.

At high temperatures both ferromagnetic and antiferromagnetic materials behave as simple

paramagnets, any magnetic coupling is broken down by thermal effects (sometimes referred
to as thermal randomisation). As the temperature is lowered, the effect of coupling can
overcome thermal randomisation and magnetic ordering is observed. This means that there
is a significant rise (ferromagnetic) or fall (anti-ferromagnetic) of the susceptibility and
magnetic moment as the coupling takes effect. The points at which this occurs are known as
the Curie point (TC, for ferromagnetic compounds) and the Néel point (T N, for
antiferromagnetic compounds).

 Magnetic crystal anisotropy: the magnetism of a single crystal may be anisotropic

 Magnetic and structural unit cell may be different
 the magnetic structure of a crystalline sample can be determined with „thermal
neutrons“ (neutrons with a wavelength in the order of magnitude of interatomic
distances): de Broglie equation: λ = h/m nvn (requires neutron radiation of a nuclear
reactor)
Magnetization of an initially „non-magnetic“ ferro- or ferrimagnet („hysteresis curve“)

M(v)S: saturation magnetization

M(v)R: remanence

HC: coercive force

Soft magnets: transformers, electromagnets, electric coils, etc.

Hard magnets: sound and videotapes, permanent magnets, etc.

Metallic soft magnets:

 α-Fe, Ni, Co and some of their alloys

 Fe – Si- and Fe – Ni – compounds and alloys (e.g. Fe / 6%Si: no α→γ-phase
transition up to 1400°C)
Ceramic soft magnets:- „Ferrites“: cubic oxide spinels or perovskites, garnets (Y 3Fe5O12)

 Spinels: the magnetic moments of ions on tetrahedral and octahedral places are anti-
parallel

Deviations from Spin-Only Behaviour

The spin-only description of magnetic moments often holds good for transition metal
compounds, but when the electrons in the metal valence shell have non-zero orbital angular
momentum then we see deviations of the observed magnetic moments from the spin only
values.

Many transition metal salts and complexes are paramagnetic due to partially filled d-
orbitals.

The experimentally measured magnetic moment (μ) can provide some important information
about the compounds themselves:

 No of unpaired electrons present

 Distinction between HS and LS octahedral complexes
 Spectral behavior, and
 Structure of the complexes
Sources of Paramagnetism:

a) Orbital motion of the electron generating ORBITAL MAGNETIC MOMENT (μ l)

b) Spin motion of the electron (on its own axis) generating SPIN MAGNETIC MOMENT
(μs)
l = orbital angular momentum; s = spin angular momentum

For multi-electron systems

L = l1 + l2 + l3 + …………….

S = s1 + s2 + s3 + ……………

μL+S = [4S(S+1)+ L(L+1)]1/2 Β.Μ.

For TM-complexes, the magnetic properties arise mainly from the exposed d-orbitals. The d-
orbitals are perturbed by ligands.

∴The rotation of electrons about the nucleus is restricted which leads to L = 0.

μs = [4S(S+1)]1/2 Β.Μ.

S = n (1/2) = n/2; n = no of unpaired electrons. Hence

μs = [4S(S+1)]1/2 Β.Μ.

= [4(n/2)(n/2+1)]1/2 Β.Μ.

= [n(n+2)]1/2 Β.Μ.

This is called Spin-Only Formula.

When does orbital angular momentum contribute?

There must be an unfilled / half-filled orbital similar in energy to that of the orbital occupied
by the unpaired electrons. If this is so, the electrons can make use of the available orbital to
circulate or move around the center of the complexes and hence generate L and μ L.

Essential Conditions:
 1. The orbitals should be degenerate (t2g or eg)
2. The orbitals should be similar in shape and size; so that they are transferable into one
another by rotation about the same axis (e.g. d xy is related to dx2-y2 by a rotation of 45o
about the z-axis.
3. Orbitals must not contain electrons of identical spin.
Table 1: Summary of Ground Terms and Orbital Contributions in First Row Transition Metal
Ions.
Number Octahedral Complexes Tetrahedral Complexes
of d
Electron Ground Orbital Electron Ground Orbital
electrons
Configuration Term Contribution Configuration Term Contribution
1 t2g1 2
T2g Yes e1 2
E No
2 t2g2 3
T1g Yes e2 3
A2 No
3 t2g3 4
A2g No e2 t21 4
T1 Yes
4 t2g3 eg1 5
Eg No
e2 t22 5
T2 Yes
t2g4 3
T1g Yes
5 t2g3 eg2 6
A1g No
e2 t23 6
A1 No
t2g5 2
T2g Yes
6 t2g4 eg2 5
T2g Yes
e3 t23 5
E No
t2g6 1
A1g No
7 t2g5 eg2 4
T1g Yes
e4 t23 4
A2 No
t2g6 eg1 2
Eg No
8 T2g6 eg2 3
A2g No e4 t24 3
T1 Yes
9 T2g6 eg3 2
Eg No e4 t25 2
T2 Yes
It can be seen that complexes with a T ground term do have an orbital angular momentum
contribution, while those with A or E ground terms do not.

Magnetic Properties of Complexes with A and E ground terms

Such complexes have no orbital contribution to the ground state, so we would expect the
magnetic moment to follow the spin-only formula. Now, it happens that for a number of the
transition metals in commonly occurring oxidation states the d-electron configurations give
rise to A or E ground terms (e.g. d 3 Cr3+; d5 (Mn2+, Fe3+), d8 (Ni2+), d9 (Cu2+)) and thus should
give magnetic moments in good agreement with the spin-only formula. This is indeed the
case in many (but not all) instances. Furthermore, since the spin-only formula does not have
a temperature dependent term, complexes with A and E ground terms are expected to show
no temperature dependence.

However, we can see from Table 2 (below) that the fit to spin-only magnetic moments is not
always good. This is because, although the ground state has no orbital contribution, excited
electronic states may have T terms, and if they have the same multiplicity these can mix with
the ground state.

If the ground term is A1 this is derived from a free ion S term and does not give rise to higher
T terms. Hence, ions with A1 ground terms fit the spin-only model very well (e.g. d 5, Mn2+).
Electron configurations with A2 ground terms (from a free ion F term) and E ground terms

  
 eff   spinonly 1  
 E 
(from a free ion D term) will have higher T terms which can mix with the ground states and
thus will show deviations from the spin only formula. In such cases the magnetic moment is
given by:

Where α = 2 for an E term and α = 4 for an A 2 term. The spin-orbit coupling constant, λ, has
a positive sign for less than half-filled d-shells and a negative sign for greater than half-filled
d-shells. ΔE is the energy of the lowest energy d-d transition in cm -1. We therefore get values
for the observed magnetic moments which are slightly larger (later transition metals) or
smaller (early transition metals) than the spin-only values. Typically the values will deviate by
a few tenths of a Bohr Magneton.

Example:

Calculate the effective magnetic moment of the [Ni(en) 3]2+ ion (en = 1,2-diaminoethane). The
lowest energy band in the electronic spectrum is at 11500 cm -1 and the spin-orbit coupling
constant is -315 cm-1.

The complex is octahedral and Ni 2+ has a 3d8 electron configuration. Thus this species has
an 3A2g ground state. Now,

  
 eff   spinonly 1  
 E 

and
 spinonly  n(n  2)

therefore since there are two unpaired electrons in an octahedral 3d 8 complex

 spinonly  2(2  2)

= 2.83 Bohr Magnetons (BM)

Since this species has an A term, α = 4. λ is negative, since there are > 5 d electrons and
therefore:

 4  315 
 eff  2.831  
 11500 

= 3.14 BM

The resulting magnetic moment is a little larger than the spin-only value.

Table 2: Magnetic Moments of Selected Compounds with A or E Ground Terms

Number Compound Geometry µeff (B.M.)
 of d
80 K 300 K Spin only
electrons
1 VCl4 Tetrahedral 1.6 1.6 1.73
3 KCr(SO4)2.12 H2O Octahedral 3.8 3.8 3.87
4 CrSO4.6 H2O Octahedral 4.8 4.8 4.90
5 K2Mn(SO4)2.6 H2O Octahedral 5.9 5.9 5.92
7 Cs2CoCl4 Tetrahedral 4.5 4.6 3.87
8 (NH4)2Ni(SO4)2.6H2O Octahedral 3.3 3.3 2.83
(NH4)2Cu(SO4)2.6H2
9 Octahedral 1.9 1.9 1.73
O

Magnetic Properties of Complexes with T Ground Terms

The magnetic behaviour of complexes with T ground terms is rather more complex. The T
terms are split by spin-orbit coupling to produce levels whose energy differences are often of
the order kT (kT  200 cm-1 at room temperature). Consequently, temperature will affect the
populations of these levels in a magnetic field, and so the magnetic moments of such
materials will vary with temperature.

It can be seen that, with one exception (V 3+) the room temperature magnetic moment is
slightly larger than the spin-only value, with the deviation being of the order of a few tenths of
a Bohr Magneton. In addition there is a small difference in the magnetic moments at 80 K
and 300 K (again, a few tenths of a Bohr magneton), confirming the temperature
dependence in these species.

Table 3: Magnetic Moments of Selected Compounds with T Ground Terms

Number µeff (B.M.)
of d Compound Geometry
electrons 80 K 300 K Spin only
1 Cs2VCl6 Octahedral 1.4 1.8 1.73
(NH4)V(SO4)2.12
2 Octahedral 2.7 2.7 2.83
H2O
4 K3[Mn(CN)6] Octahedral 3.1 3.2 2.83
5 K3[Fe(CN)6] Octahedral 2.2 2.4 1.73
6 (NH4)2Fe(SO4)2.6H2O Octahedral 5.4 5.5 4.90
(NH4)2Co(SO4)2.6H2
7 Octahedral 4.6 5.1 3.87
O
8 (Et4N)2NiCl4 Tetrahedral 3.2 3.8 2.83

Magnetic Properties of lanthanides

See section on lanthanides

Superexchange

In order for a material to be magnetically ordered, the spins on one atom must couple with
the spins on neighboring atoms. The most common mechanism for this coupling (particularly
in insulators) is through the semicovalent superexchange interaction. The spin information is
transferred through covalent interactions with the intervening ligand (say oxygen).

Gh