3/21/2020 Introduction to Magnetochemistry

Introduction to Magnetochemistry
David Young
Cytoclonal Pharmaceutics Inc.

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.
This includes synthesis, analysis and understanding. This short description is meant to give a basic
understanding before you delve into a more complex treatment.

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

1. Nuclear spin. Some nuclei, such as a hydrogen atom, have a net spin which creates a magnetic field.

2. Electron spin. An electron has two intrinsic spin states (similar to a top spinning) which we call up and
down or alpha and beta.

3. Electron orbital motion. There is a magnetic field due to the electron moving around the nucleus.

Each of these magnetic fields interact with one another and with external magnetic fields. However, some of
these interactions are strong and others are negligible.

Measurement of interactions with nuclear spins are used to analyze compounds in nuclear magnetic resonance
(NMR) and electron spin resonance (ESR) spectroscopy. In most other situations, interaction with nuclear spins
is a very minor effect.

Interactions between the intrinsic spin of one electron and the intrinsic spin of another electron are strongest for
very heavy elements such as the actinides. This is called spin-spin coupling. For these elements this coupling can
shift the electron orbital energy levels.

The interaction between an electron's intrinsic spin and it's orbital motion is called spin-orbit coupling. Spin-
orbit coupling has a significant effect on the energy levels of the orbitals in many inorganic compounds.

Macroscopic effects, such as the attraction of a piece of iron to a bar magnet are primarily due to the number of
unpaired electrons in the compound and their arrangement. The various possible cases are called magnetic states
of matter.

Magnetic States of Matter

Diamagnetic - A diamagnetic compound has all of it's electron spins paired giving a net spin of zero.
Diamagnetic compounds are weakly repelled by a magnet.

Paramagnet - A paramagnetic compound will have some electrons with unpaired spins. Paramagnetic
compounds are attracted by a magnet.

Ferromagnet - In a ferromagnetic substance there are unpaired electron spins, which are held in alignment by a
process known as ferromagnetic coupling. Ferromagnetic compounds, such as iron, are strongly attracted to
magnets.
www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 1/8
3/21/2020 Introduction to Magnetochemistry

Ferrimagnet - Ferrimagnetic compounds have unpaired electron spins, which are held in an pattern with some
up and some down. This is known as ferrimagnetic coupling. In a ferrimagnetic compound, there are more spins
held in one direction, so the compound is attracted to a magnet.

Antiferromagnetic - When unpaired electrons are held in an alignment with an equal number of spins in each
direction, the substance is strongly repelled by a magnet. This is referred to as an antiferromagnet.

Superconductor - Superconductors are repelled by magnetic fields because the magnetic field is excluded from
passing through them. This property of superconductors, called the Meissner effect, is used to test for the
presence of a superconducting state. The underlying theory of how superconductivity arises is still a matter of
much research and debate at the time of this writing. It does appear that the mechanism behind the magnetic
properties of superconductors is significantly different from the other classes of compounds discussed here. For
these reasons, superconductors will not be discussed further here.

Interaction with an External Magnetic Field

A magnetic field is given the symbol "H" which is a vector since the field has both a direction and a magnitude.
For this discussion we will consider only interactions in one dimension making H and many other quantities we
will define scalars. This gives us results for a homogeneous magnetic field and is a very good approximation for
the way that most magnetic property measurements are performed. The magnitude of the magnetic field is
usually given in units of gauss (G) or tesla (T) where 1 tesla = 10000 gauss.

When a material is placed in a magnetic field, the magnetic field inside the material will be the sum of the
external magnetic field and the magnetic field generated by the material itself. The magnetic field in a material is
called the magnetic induction and given the symbol "B". The formula for this is
B = H + 4 Pi M

where

B = magnetic induction
H = external magnetic field
Pi = 3.14159
M = magnetization ( a property of the material )

For mathematical and experimental convenience this equation if often written as

B = 1 + 4 Pi M = 1 + 4 Pi Xv
- ------
H H

where

Xv = M/H = volume magnetic susceptibility

The volume magnetic susceptibility is so named because B, H and M are defined per unit volume. However this
results in Xv being unitless. It is convenient to use the magnetic susceptibility instead of the magnetization
because the magnetic susceptibility is independent of the magnitude of the external magnetic field, H, for
diamagnetic and paramagnetic materials.

Many studies are done using Xg, magnetic susceptibility per gram, which is Xv divided by the density. This
gives units of cm cubed per gram.

Another useful form is Xm, molar magnetic susceptibility, which is Xg times the molecular weight. This gives
units of cm cubed per mole.

Another measure of magnetic interaction that is often used is an effective magnetic moment, mu, where
www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 2/8
3/21/2020 Introduction to Magnetochemistry

mu = 2.828 ( Xm T )1/2

where

mu = effective magnetic moment

Xm = molar magnetic susceptibility
T = temperature

The numeric factor puts mu in units of Bohr magnetons (BM). Where one BM equals 9.274 x 10^-24 joules per
tesla. The effective magnetic moment is a convenient measure of a material's magnetic properties because it is
independent of temperature as well as external field strength for diamagnetic and paramagnetic materials.

This said, we would now like to examine how the magnetization, magnetic susceptibility and effective magnetic
moment depend on molecular structure.

Diamagnetism
Diamagnetism can be described by electrons forming circular currents, orbiting the nucleus, in the presence of a
magnetic field. As such, a diamagnetic contribution can be calculated for any atom. However, the magnitude of
the diamagnetic contribution is so much smaller than the magnitude of paramagnetic and other effects that it is
usually ignored for any other type of materials.

In this orbital model, the diamagnetic susceptibility from a given electron is proportional to the square of it's
mean distance from the nucleus. Thus larger atoms are expected to have a larger diamagnetic interaction than
smaller atoms. Often, the contributions for common atoms are tabulated along with corrections for multiple
bonds. Thus a magnetic susceptibility can be predicted merely by adding together the contributions from all of
the atoms and bonds in the molecule. For an example of these scheme, see Drago. For a more complete
treatment, see Selwood.

Paramagnetism

The structural feature most prominent in determining paramagnetic behavior is the number of unpaired electrons
in the compound. A spin only formula for the magnetic moment of a paramagnetic compound is

mu = g { S ( S + 1 ) }1/2

where

mu = effective magnetic moment

g = 2.0023
S = 1/2 for one unpaired electron
1 for two unpaired electrons
3/2 for three unpaired electrons, etc.

This equation is sometimes written with g=2. This does not introduce a significant error since this simple spin
only treatment is a decent approximation but is often not accurate even to two significant digits.

An equation which takes into account both spin and orbital motion of the electrons is

mu = { 4 S ( S + 1 ) + L ( L + 1 ) }1/2

where

mu = effective magnetic moment

S = 1/2 for one unpaired electron, 1 for two, etc.
L = total orbital angular momentum

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 3/8
3/21/2020 Introduction to Magnetochemistry

This equation is derived for atoms. It is applicable only to molecules with very high symmetry where the
energies of the orbitals containing unpaired electrons are degenerate. A discussion of the calculation of "L" can
be found in any introductory quantum mechanics text or in the chapter on quantum mechanics in many physical
chemistry texts.

If the splitting of orbital energy levels is large relative to k T ( k is the Boltzman constant ) then the applicable
formula is

mu = g { J ( J + 1 ) }1/2

where

g = 1 + S ( S + 1 ) - L ( L + 1 ) + J ( J + 1 )
---------------------------------------
2 J ( J + 1 )

where

J = S + L

This formula is usually used for the lanthanide and actinide elements. For more accurate treatment of these
elements, a diamagnetic contribution can be added to this as described by Selwood.

If the splitting of orbital energy levels is comparable in magnitude to k T then the expression for magnetic
properties must incorporate a Boltzman distribution. This is often the case with high spin transition metal
complexes. The worst case, where this procedure is absolutely imperative, is the description of spin cross overs
such as exhibited by some iron coordination compounds. Examples of this type of treatment are given in both
the Drago and Selwood texts.

For all of the cases of paramagnetic behavior the spin only formula is often used as a first rough approximation.
If the only purpose for measuring the magnetic susceptibility is to determine the number of unpaired electrons
this is often all that is done.

Ferromagnetism, Antiferromagnetism and Ferrimagnetism

The advantage of using effective magnetic moments for describing paramagnetic behavior is that it is a measure
of the materials magnetic behavior which is not dependent upon either the temperature or the magnitude of the
external field. It is not possible to set up such a convention for ferromagnetic, antiferromagnetic and
ferrimagnetic materials.

All three of these classes of materials can be considered a special case of paramagnetic behavior. The description
of paramagnetic behavior is based on the assumption that every molecule behaves independently. The materials
discussed here result from a situation in which the direction of the magnetic field produced by one molecule is
affected by the direction of the magnetic field produced by an adjacent molecule, in other words their behavior is
coupled. If this occurs in a way in which the magnetic fields all tend to align in the same direction, a
ferromagnetic material results and the phenomenon is called ferromagnetic coupling. Antiferromagnetic
coupling gives an equal number of magnetic fields in opposite directions. Ferrimagnetic coupling gives magnetic
fields in two opposite orientations with more in one direction than in the other.

With a few exceptions, the magnetic moments are not aligned through out the entire material. Typically regions,
called domains, will form with different orientations. The existence of domains of coupled molecules gives rise
to a number of types of behavior as described in the following paragraphs.

The tendency of molecules to align themselves to one another enhances the magnetization of the material due to
the presence of an external magnetic field. This is why ferromagnetic and ferrimagnetic materials can have
magnetic susceptibilities several orders of magnitude large than paramagnetic materials. This also gives rise to

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 4/8
3/21/2020 Introduction to Magnetochemistry

the fact that the magnetic susceptibility of these materials is not independent of the magnitude of the external
magnetic field as was the case for diamagnetic and paramagnetic materials.

For a ferromagnetic material, the actual field acting on a given magnetic dipole ( unpaired electron ) is
designated Ht and given by an equation similar to the equation for magnetic induction given above.

Ht = H + Nw M

where

Ht = magnetic field felt by an electron

H = external magnetic field
Nw = molecular field constant, approximately 10000
M = magnetization

This equation is used because it allows a mathematical treatment of a ferromagnetic substance similar to that
used for paramagnetic substances. In this form the molecular field constant, Nw, is typically defined empirically
in order to take the ferromagnetic coupling into account. To obtain the molecular field constant in a rigorous way
would require a quantum mechanical calculation that takes into account the elements, their arrangement in the
solid, kinetic energy of the electrons, coulombic attraction of electrons to the nucleus and repulsion with other
electrons as well as spin interactions. What is most often done is a computer simulation using the Ising model,
which is not truly rigorous but is based on quantum mechanics. This is a spin only quantum mechanical
treatment assuming that the values of neighboring spins can be replaced by their average over time. For more
explanation, see Morrish.

Vibrational motion of the molecules, which increases with temperature, can disrupt the domain structure. Thus
the magnetic properties of all three of these types of materials are strongest at low temperatures. At sufficiently
high temperatures, no domain structure is able to form so all of these materials become paramagnetic at high
temperatures. The temperature at which paramagnetic behavior is seen called the Curie temperature for
ferromagnetic and ferrimagnetic materials and called the Neel temperature for antiferromagnetic materials. This
is why a temperature independent effective magnetic moment cannot be defined for these materials.

The alignment of the magnetic moments of the domains may give the material a net magnetic moment even in
the absence of an external field. This gives a permanent magnet, such as a bar magnet. A material with no net
moment prior to being exposed to an external magnetic field may retain a net moment after being exposed to an
external magnetic field. This is how cassette and video tapes and computer disks store information. The
magnitude of this memory effect can be quantified by plotting magnetization vs field strength as the external
field intensity is varied from one polarity to the other and back again. A strong memory effect will be indicated
by a wide hysteresis loop.

Over a period of time magnetic domains tend to return to a random orientation. This makes the kinetics of this
relaxation process another factor in the magnetic behavior of these materials. This is also responsible for the
limited life span of magnetically stored music, video and computer data.

Variation with Temperature

The source of variation of magnetic properties with temperature is the disruption of the alignment of molecular
magnetic moments due to the thermal motion of the atoms. As such, it should come as no surprise that
diamagnetic behavior shows no variation with temperature.

Paramagnetism
As temperature increases, the magnetic susceptibility of a paramagnetic substance decreases.

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 5/8
3/21/2020 Introduction to Magnetochemistry

In some paramagnetic compounds the magnetic susceptibility is inversely proportional to the temperature. These
are called "normal paramagnets" and have magnetic properties arising primarily due to the presence of
permanent magnetic dipoles. This is referred to as the Curie Law and is expressed in mathematical form as

X = C / T

where

C = Na g2 b2
-------
4 k

where

X = magnetic susceptibility
C = the Curie constant
T = temperature
Na = Avogadro's number
g = the electron g factor
b = the Bohr magneton
k = the Boltzman constant

In most paramagnetic compounds, an inverse relationship is observed, but the extrapolation to zero temperature
does not obey the Curie Law. These compounds obey the Curie-Weiss Law which is

X = C
---------
T - theta

where theta is a constant referred to as the Weiss constant. The Weiss constant can have a large range of values
from -70 K to 3000 K. Most often it is positive.

Ferromagnetism & ferrimagnetism

Ferromagnetic and ferrimagnetic compounds also show a decrease in magnetic susceptibility with increasing
temperature. However, a plot of magnetic susceptibility vs. temperature shows a different line shape for these
compounds than for paramagnetic compounds. This plot would have a positive curvature for paramagnetic
compounds and a negative curvature for ferromagnetic compounds. A rough sketch of the shapes of these curves
is as follows

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 6/8
3/21/2020 Introduction to Magnetochemistry

When a critical temperature ( called the Curie temperature ) is reached, the curvature of the plot changes. At the
Curie temperature, ferromagnetic and ferrimagnetic compounds become paramagnetic. Curie temperatures range
from 16 C for Gd to 1131 C for Co.

For ferromagnetic substances a universal temperature curve can be constructed, meaning that all substances with
the same total spin follow the same curve. This is done by plotting M(T)/M(0) vs T/Tc where M(T) is the
magnetization at a given temperature, M(0) is the magnetization at absolute zero, T is the temperature and Tc is
the Curie temperature. For more information, see Morrish.

Antiferromagnetism
Antiferromagnetic compounds show an increase in magnetic susceptibility until their critical temperature, called
the Neel temperature, is reached. Above the Neel temperature these compounds also become paramagnetic. Neel
temperature range from 1.66 K for MnCl2*4H2O to 953 K for alpha-Fe2O3.

As with ferromagnetic substances, a universal temperature curve can be constructed that all substances with the
same number of unpaired electrons follow. This is done by plotting X(T)/X(Tn) vs T/Tn where X(T) is the
magnetic susceptibility at a given temperature, X(Tn) is the magnetic susceptibility at the Neel temperature, T is
the temperature and Tn is the Neel temperature. For more information, see Morrish.

Further Information
Magnetochemistry is most often the realm of inorganic chemists so there should be a short discussion in any
basic inorganic text.

An old but good book on many aspects of magnetochemistry is

P. W. Selwood "Magnetochemistry" Interscience (1956)

Another good text is

A. H. Morrish "The Physical Principles of Magnetism" John Wiley & Sons (1965)

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 7/8
3/21/2020 Introduction to Magnetochemistry

There are chapters on magnetochemistry in

R. S. Drago "Physical Methods For Chemists" Saunders College and Harcourt Brace Jovanovich (1992)
L. Solymar, D. Walsh "Lectures on the Electrical Properties of Materials" Oxford (1993)

A mathematical treatment can be found in

D. L. Goodstein "States of Matter" Dover (1985)

Solid state properties are covered in

A. R. West "Solid State Chemistry and its Applications" John Wiley & Sons (1992)

A book describing more sophisticated simulation techniques is

M. H. Krieger "Constitutions of Matter" University of Chicago Press (1996)

Return to table of contents.

www.ccl.net/cca/documents/dyoung/topics-orig/magnet.html 8/8