Diamagnetism and paramagnetism
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Diamagnetism and Paramagnetism. Physics 355. Free atoms… The property of magnetism can have three origins: Intrinsic angular momentum (Spin) Orbital angular momentum about the nucleus Change in the dipole moment due to an applied field.

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Diamagnetism and paramagnetism

Diamagnetism and Paramagnetism

Physics 355


Diamagnetism and paramagnetism

  • Free atoms…

  • The property of magnetism can have three origins:

  • Intrinsic angular momentum (Spin)

  • Orbital angular momentum about the nucleus

  • Change in the dipole moment due to an applied field

In most atoms, electrons occur in pairs. Electrons in a pair spin in opposite directions. So, when electrons are paired together, their opposite spins cause their magnetic fields to cancel each other. Therefore, no net magnetic field exists. Alternately, materials with some unpaired electrons will have a net magnetic field and will react more to an external field.


Diamagnetism classical approach

B

v

E

Diamagnetism: Classical Approach

Consider a single

closed-shell atom

in a magnetic field.

Spins are all paired and

electrons are distributed

spherically around the

atom. There is no

total angular

momentum.

nucleus

r

electron


Diamagnetism larmor precession

B

Lorentz Force

F = -e(v x B)

F = eBrw

Diamagnetism: Larmor Precession

nucleus

r

v, w0

electron


Diamagnetism and paramagnetism

Diamagnetism: Quantum Approach

starting

point

Quantum mechanics makes some useful corrections. The components of L and S are replaced by their corresponding values for the electron state and r2is replaced by the average square of the projection of the electron position vector on the plane perpendicular to B, which yields

where R is the new radius of the sphere.


Diamagnetism and paramagnetism

Diamagnetism: Quantum Approach

If B is in

the z direction


Diamagnetism and paramagnetism

Diamagnetism: Quantum Approach

  • The atomic orbitals are used to estimate <x2 + y2>.

  • If the probability density *  for a state is spherically symmetric <x2> = <y2>= <z2> and <x2 + y2>=2/3<r2>.

  • If an atom contains Z electrons in its closed shells, then

Consider a single

closed-shell atom

in a magnetic field.

Spins are all paired and

electrons are distributed

spherically around the

atom. There is no

total angular

momentum.

  • The B is the local field at the atom’s location. We need an expression that connects the local field to the applied field. It can be shown that it is


Diamagnetism and paramagnetism

Diamagnetism

Core Electron

Contribution

  • Diamagnetic susceptibilities are nearly independent of temperature. The only variation arises from changes in atomic concentration that accompany thermal expansion.


Diamagnetism and paramagnetism

ccp structure

Diamagnetism: Example

Estimate the susceptibility of solid argon. Argon has atomic number 18; and at 4 K, its concentration is2.66 x 1028 atoms/m3. Take the root mean square distance of an electron from the nearest nucleus to be 0.62Å. Also, calculate the magnetization of solid argon in a 2.0 T induction field.


Diamagnetism and paramagnetism

ccp structure

Diamagnetism: Example

Estimate the susceptibility of solid argon. Argon has atomic number 18; and at 4 K, its concentration is2.66 x 1028 atoms/m3. Take the root mean square distance of an electron from the nearest nucleus to be 0.62Å. Also, calculate the magnetization of solid argon in a 2.0 T induction field.


Paramagnetism

Paramagnetism


Diamagnetism and paramagnetism

Core Paramagnetism

If <Lz> and <Sz> do not both vanish for an atom, the atom has a permanent magnetic dipole moment and is paramagnetic.

Some examples are rare earth and transition metal salts, such as GdCl3 and FeF2. The magnetic ions are far enough apart that orbitals associated with partially filled shells do not overlap appreciably. Therefore, each magnetic ion has a localized magnetic moment.

Suppose an ion has total angular momentum L, total spin angular momentum S, and total angular momentum J = L + S.


Diamagnetism and paramagnetism

Core Paramagnetism

Landé g factor


Diamagnetism and paramagnetism

Hund’s Rules

  • For rare earth and transition metal ions, except Eu and Sm, excited states are separated from the ground state by large energy differences – and are thus, generally vacant.

  • So, we are mostly interested in the ground state.

  • Hund’s Rules provide a way to determine J, L,and S.

  • Rule #1: Each electron, up to one-half of the states in the shell, contributes +½ to S. Electrons beyond this contribute  ½ to S. The spin will be the maximum value consistent with the Pauli exclusion principle.

Frederick Hund

1896-1997


Diamagnetism and paramagnetism

Hund’s Rules

  • Each d shell electron can contribute either 2, 1, 0, +1, or +2 to L.

  • Each f shell electron can contribute either 3, 2, 1, 0, +1, +2, or +3 to L.

  • Two electrons with the same spin cannot make the same contribution.

  • Rule #2: L will have the largest possible value consistent with rule #1.


Diamagnetism and paramagnetism

Hund’s Rules

  • Rule #3:


Diamagnetism and paramagnetism

Hund’s Rules: Example

Find the Landég factor for the ground state of a praseodymium (Pr) ion with two f electrons and for the ground state of an erbium (Er) ion with 11 f electrons.

  • Pr

  • the electrons are both spin +1/2, per rule #1, so S= 1

  • per rule #2, the largest value of Loccurs if one electron is

  • +3 and the other +2, so L = 5

  • now, from rule #3, since the shell is less than half full,


Diamagnetism and paramagnetism

Hund’s Rules: Example

Find the Landég factor for the ground state of a praseodymium (Pr) ion with two f electrons and for the ground state of an erbium (Er) ion with 11 f electrons.

  • Er

  • per rule #1, we have 7(+1/2) and 4(1/2), so S= +3/2

  • per rule #2, we have 2(+3), 2(+2), 2(+1), 2(0), 1(1), 1(2), and 1(3), so L = 6

  • now, from rule #3, since the shell is more than half full,

  • J = L + S = 15/2


Diamagnetism and paramagnetism

Paramagnetism

  • Consider a solid in which all of the magnetic ions are identical, having the same value of J (appropriate for the ground state).

    • Every value of Jz is equally likely, so the average value of the ionic dipole moment is zero.

    • When a field is applied in the positive z direction, states of differing values of Jz will have differing energies and differing probabilities of occupation.

    • The z component of the moment is given by:

    • and its energy is


Diamagnetism and paramagnetism

Brillouin

Function

As a result of these probabilities, the average dipole moment is given by


Diamagnetism and paramagnetism

J(x)

x

Brillouin Function


Diamagnetism and paramagnetism

Paramagnetism


Diamagnetism and paramagnetism

Paramagnetism

Curie Law

The Curie constant can be rewritten as

where p is the effective number of Bohr magnetons per ion.


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