Magnetic properties of solids

macroscopic definitions
magnetization & susceptibility
new terms in Hamiltonian
diamagnetism, paramagnetism
Hund's rules, Curie's law
Pauli paramagnetism
Heisenberg Hamiltonian
ferro-, ferri-, antiferromagnetism, spin-spirals,
Weiss exchange field & mean-field theory
spin waves & magnons (A&M)
 Macroscopic definitions
Thermodynamics: free energy

Magnetization

Susceptibility

Force in inhomogeneous magnetic field

 Electrons in magnetic field
change of canonical momentum operator

the kinetic energy operator becomes

add interaction of spins with magnetic field

summary of new terms in Hamiltonian

 Perturbation theory
the new terms are small at fields which we can
produce in laboratories, therefore we treat it
as a perturbation

susceptibility is 2nd order in H

changes in energy levels up to 2 nd order in H:

the linear term is of the order of ~1 meV in

fields ~10 T, the other terms are 3-4 orders of
magnitude smaller
 Larmor diamagnetism
insulators, closed shells in ground state
(L=S=J=0), i.e., only last term contributes
ground-state energy change due to mag. field:

if all excited states are high in energy, then

This is Larmor diamagnetic susceptibility

(negative), typically ~10-5
 Hund's rules
(1) Maximize the total spin S.
A.k.a. the bus seat rule.
Maximizing spin reduces screening and allows
electrons to get closer to cores.
(2) While fulfilling (1), maximize the total orbital
momentum L.
Classically: orbiting in the same direction reduces
probability that electrons meet, i.e., reduces repulsion.
(3) For less than half-filled shells J = |L-S| and for
more than half-filled shells J = L + S.
This is a consequence of spin-orbit coupling
 Van-Vleck paramagnetism
if J=0, but not L or S, the first term vanishes

we get two non-zero terms in susceptibility

first term is Larmor diamagnetism

second term is Van-Vleck paramagnetism
(positive)
if the first excited state is close in energy to the
ground state, more complicated formulas apply
 Paramagnetism
For atoms with unfilled shells with nonzero S, L
and J, the first term is nonzero and dominates
We have (2J+1) degenerate state in zero field
In nonzero field we need to diagonalize
(2J+1)x(2J+1) matrix with elements

Wigner-Eckart theorem states

with Land factor

 Paramagnetism
Thanks to Wigner-Eckart theorem we see that
the matrix is actually diagonal

we can interpret (within the lowest J-multiplet)

as a magnetic moment of the ion

To get susceptibility we need to consider all
these (2J+1) states split by magnetic field
Free energy
 Brillouin function
From free energy we get magnetization

where Brillouin function is defined by

At low temperatures BJ=1

At high temperatures
 Curie's law
At high temperatures we get for susceptibility

i.e., susceptibility is inverse-proportional to

temperature Curie-Weiss law
This paramagnetic susceptibility is at room
temperature of the order of 10 -2-10-3 and thus
dominates the diamagnetic contribution
Effective moment / effective Bohr magneton
number p:
 Example: rare-earth paramagnets

Good agreement
theory-experiment,
except for Sm & Eu
Sm & Eu have low-
lying excited states,
which we neglected
 Example: 3d transition metals
For 3d transition
metals Curie's law
works if we
assume L=0
Quenching of orbital
momentum due to
crystal field
splitting
Modification of the
third Hund's rule
 Magnetism of conduction electrons
Delocalized conduction electrons
Magnetic field shifts energy levels by
Since we can expand density of states

and obtain for number of occupied states

i.e., the magnetization is

 Pauli paramagnetism
From magnetization

we get a susceptibility

which is independent of temperature

This contribution is called Pauli paramagnetism
-6

It is of order 10 , i.e., comparable to Larmor

diamagnetic contribution
Note: conduction electrons also have Landau
diamagnetic contribution to susc., see A&M
 Interactions of magnetic moments
So far we considered the moments of ions as
independent, i.e., magnetization appeared only
in external field, otherwise thermal fluctuations
lead to zero mean value of magnetization
Adding interactions explains nonzero M even in
zero external field, e.g., magnetite
What interactions? Dipolar, spin-orbital, electro-
static, ...
Dipolar (~0.1meV) & spin-orbital interactions
are typically much weaker than electro-static
interactions + Pauli principle (~1eV)
 Hydrogen molecule
Two electron system, four possible spin arrangements

We can classify them as

spin singlet (S=0) and
spin triplet (S=1):
The ground state is singlet
If we neglect all the higher excited states and restrict
ourselves to singlet & triplet, we can reproduce the
energy levels by the following model Hamiltonian
expressed in spin-space only:
 Heisenberg model
Generalization of the situation with hydrogen
molecule:
Extracting Jij is not a trivial problem and to
some extent it is still not completely solved
Mechanisms/sources of Jij:
Direct exchange
Super-exchange
Indirect exchange (RKKY)
Itinerant exchange
 Magnetic structures
J>0 for nearest neighbors ferromagnet
J<0 for nearest neighbors antiferromagnet
non-negligible J's for more distant neighbors or
in geometries leading to magnetic frustrations
more complicated magnetic structures, e.g.,
spin spirals, non-collinear structures, etc.
 Mean-field theory Weiss field
rewrite the Heisenberg model, including field:

this looks like a set of spins in effective field

which does not depend on i due to periodicity

yet, the effective (Weiss) field is an operator
the mean-field theory replaces it with its
thermodynamic mean value
 Critical temperature
Taking mean-field approximation and zero
external field we obtain equation

When M(T) goes to zero, and we get

the mean-field approximation of the magnetic

transition temperature
Weak points: over-estimation of TC, wrong low-
temperature behavior, also around TC
 More advanced methods
Random-phase approximation

Monte-Carlo simulations exact answers within

the Heisenberg model, though demanding
calculations
Using numerical methods we can also get M(T)
within all three methods
Doing Monte-Carlo Heisenberg model
quantum-mechanically is still an active field of
research