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Source: “Physical Methods for Chemists” R. S. Drago, Surfside, Gainsville, FL, 1992.
• Diamagnetism arises from the circulation of paired electrons within the species to
generate a weak magnetic dipole aligned parallel to the external magnetic field.
Source: Ege, “Organic Chemistry, 2nd Ed.”, D. C. Heath and Co., 1989, Lexington, MA
Section 5.2 - 1
• Since all atom-based matter has some paired electrons, all atom-based matter will
exhibit a diamagnetic response to an applied magnetic field…HOWEVER...that
response is very small and will be overridden by any other magnetic properties that
may arise if the matter also has unpaired electrons (i.e., is paramagnetic).
Step-by-Step:
Macroscopic (bulk) magnetic properties related to microscopic (atomic) principles
II. The total magnetic induction B within a substance is proportional to the sum of
the applied magnetic field H and the magnetization M of the substance:
! !
B ⎛ M ⎞
! = µ 0 ⎜⎜1 + ! ⎟⎟
H ⎝ H ⎠
Section 5.2 - 2
It is more useful to use the molar magnetic susceptibility (χ), related by dividing
the volume magnetic susceptibility by the density of the material and multiplying
by molecular weight. This is the magnetic susceptibility per mole:
χ = χ volume × MW ÷ ρ
χ is expressed in units of cm3 mol-1
or alternatively in emu/mol
NOTE: From now on, we will consider the magnetization M to mean the molar
magnetization and reference to magnetic susceptibility will imply molar magnetic
susceptibility.
However, many authors express H in gauss (G) which is strictly speaking a unit
of magnetic induction B created by the magnetic field.
Section 5.2 - 3
• In the cgsemu system of units, energy is expressed in erg (1 erg = 10-7 J):
Using these common units, the constant Nβ2/3kB that appears in the Curie law (for
future reference) is equal to 0.125048612 emu/mol ≈ 1/8
Section 5.2 - 4
Section 5.2 - 5
IV. Types of Magnetism ...
There are many different types of magnetism. Each corresponds to a unique set of
characteristics that can be observed by measuring the magnetic susceptibility χ of
a bulk sample as a function of temperature and applied magnetic field.
The most common types of magnetism are classified based on the measured
magnetic susceptibility χ as a function of two factors:
1) temperature (T)
2) applied magnetic field (Ho)
Source: Drago
Section 5.2 - 6
Diamagnetism
• Of these, χpara is typically the largest in magnitude and responsible for the
majority of the magnetic character of a material. (NOTE: Most authors
assume that χpara is implied when discussing “χ”.)
• In order to extract χpara from χexp, we must first account for contributions from
χdia. There are a number of acceptable ways of doing this.
Section 5.2 - 7
Source: Molecular Magnetism, Olivier Kahn, 1992.
Section 5.2 - 8
V. Temperature independent paramagnetism (χTIP) is usually small – often the
same order of magnitude as χdia but opposite in sign (i.e., positive).
• In some cases, the diamagnetic (i.e., non-degenerate) ground state may couple
with a degenerate excited state (through a Zeeman perturbation...see Van
Vleck equation ahead), as long as the energy gaps are not too large. THIS IS
NOT A THERMAL POPULATION OF EXCITED STATES!
Consider sodium metal: free electrons in the 3s band and positively charged,
essentially diamagnetic ions with a [Ne] core make up the lattice points.
• When a magnetic field is applied, there is tendency for the magnetic dipoles
associated with the intrinsic spin of the free electrons to align themselves
parallel to the field, giving a positive magnetic moment.
• The electrons in a metal do not have a Boltzmann distribution (so we can’t use
the Langevin formula to calculate the magnetic susceptibility...see notes
ahead). The Fermi-Dirac distribution function must be used instead...and
since this varies little with temperature (Recall: it varies only with enormous
changes in T), the susceptibility turns out to be practically independent of
temperature!!
• Let’s derive an expression for the Pauli paramagnetism using a model metal in
which all electrons are spin paired (i.e., all energy levels are filled by two
electrons of opposite spin) and the temperature is absolute zero (i.e., the Fermi
surface is flat)...
Section 5.2 - 9
Note:
In this diagram, W is energy, so
dn/dW is the density of states
(DOS).
When a magnetic field H is applied, an electron can only flip its spin magnetic dipole
from anti-parallel to parallel if the decrease in its magnetic energy (2βH) is sufficient to
supply the extra kinetic energy required to raise it to an empty translational energy level.
(RECALL: β is the Bohr magneton...the intrinsic magnetic moment of an electron)
Another way of saying this is that the application of H lowers the energy of the spin
parallel states by an amount 2βH.
The total magnetic moment of the system is 2xβ, where x is the number of electrons
transferred from the anti-parallel to the parallel orientation...
...note that it is 2x times the Bohr magneton because flipping a spin creates both one more
spin parallel AND one less spin anti-parallel...so net effect is 2x.
2 xβ
The volume magnetic susceptibility is then χ =
µo H
• To flip an electron’s spin from antiparallel to parallel requires that its kinetic
energy be increased by w, since we may take an electron from the topmost
filled level and put it in the next highest level, which is vacant.
Section 5.2 - 10
• To flip the second electron requires an additional kinetic energy of 3w, since
the next two levels with parallel orientation are already filled. The third
electron must be given extra energy equal to 5w, and so forth.
• For the xth electron, the excess kinetic energy will be (2x-1)w.
2β 2
• Substituting this into the above equation, we get χ =
µo w
• This still doesn’t help us much until we can estimate the value of w.
• Since two electrons with spins anti-parallel to one another can occupy each
kinetic energy level, the number of such levels in the range W to W + dW is
½(dn), where dn is the number of electrons in this range.
• Hence the energy separation w between successive levels at the top of the
Fermi distribution is dW / ½(dn) = 2 (dn / dW)F-1
(where WF is the Fermi energy)
β 2 ⎛ dn ⎞
Therefore χ = ⎜ ⎟
µo ⎝ dW ⎠ F
3nβ 2
• Thus χ =
2 µoWF
Pauli was the first to derive this expression. Notice that temperature doesn’t
factor into the equation, hence the temperature independence of Pauli
paramagnetism!
Section 5.2 - 11
• It was later shown by Landau that the effect of the magnetic field on the
translational motion of the free electrons gives a diamagnetic contribution to
the susceptibility, whose value is just -1/3 of the Pauli paramagnetism
originally calculated as above. Therefore the net volume Pauli paramagnetism
effect is
nβ 2
χ Pauli =
µoWF
So now we have dealt with the diamagnetic contribution χdia and the possible types of
temperature independent contributions, χPauli and χTIP (which we will look at in more
detail when we derive the van Vleck equation)...
Section 5.2 - 12