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Magnetism in Chemistry. General concepts. There are three principal origins for the magnetic moment of a free atom: The spins of the electrons. Unpaired spins give a paramagnetic contribution. The orbital angular momentum of the electrons about the nucleus also contributing to paramagnetism.

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General concepts
General concepts

  • There are three principal origins for the magnetic moment of a free atom:

  • The spins of the electrons. Unpaired spins give a paramagnetic contribution.

  • The orbital angular momentum of the electrons about the nucleus also contributing to paramagnetism.

  • The change in the orbital moment induced by an applied magnetic field giving rise to a diamagnetic contribution.


  • = M/H

M is the molar magnetic moment

H is the macroscopic magnetic field intensity


  • In general  is the algebraic sum of two contributions associated with different phenomena:

     = D + P

D is diamagnetic susceptibility

P is paramagnetic susceptibility


Curie paramagnetism
Curie paramagnetism

Energy diagram of an S=1/2 spin in an external magnetic field along the z-axis

E = gmBH, which for g = 2 corresponds to about 1 cm-1 at 10000G


Brillouin function
Brillouin Function

M = N SmnPn = N (m½P½ + m-½P-½)

mn= -msgmB, Pn= Nn/N with S Nn



Brillouin function2
Brillouin Function

  • Substituting for P we obtain the Brillouin function



Curie law
Curie Law

where C = Ng2mB2/(4kB) is the Curie constant

Since the magnetic susceptibility is defined as  = M/H

the Curie Law results:


vs. T plot

1/ = T/C gives a straight line of gradient C-1 and intercept zero

T = C gives a straight line parallel to the X-axis at a constant value of T

showing the temperature independence of the magnetic moment.


Curie weiss paramagnetism
Curie-Weiss paramagnetism

q is the Weiss constant


Curie weiss paramagnetism1
Curie-Weiss paramagnetism

Plots obeying the Curie-Weiss law with a negative Weiss constant


Curie weiss paramagnetism2
Curie-Weiss paramagnetism

Plots obeying the Curie-Weiss law with a positive Weiss constant


Ferromagnetism
Ferromagnetism

J positive with spins parallel below Tc


Antiferromagnetism
Antiferromagnetism

  • J negative with spins antiparallel below TN


Ferrimagnetism
Ferrimagnetism

  • J negative with spins of unequal magnitude antiparallel below critical T


Spin hamiltonian in cooperative systems
Spin Hamiltonian in Cooperative Systems

This describes the coupling between pairs of individual spins, S, on atom i and atom j with J being the magnitude of the coupling


Magnetisation
Magnetisation

Knowing how M depends on B through the Brillouin function and assuming that B = 0 we can plot the two sides of the equation as functions of M/T











Superparamagnets
SUPERPARAMAGNETS

  • These are particles which are so small that they define a single magnetic domain.

  • Usually nanoparticles with a size distribution

  • It is possible to have molecular particles which also display hysteresis – effectively behaving as a Single Molecule Magnet (SMM)


Mn12

Orange atoms are Mn(III) with S = 2, green are Mn(IV) with S = 3/2





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