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Germano Maioli Penello
Chapter 7
Magnetism in the localised electron model
Presentation based on the bookMagnetism: Fundamentals, Damien Gignoux & Michel Schlenker
Magnetism of a free atom or ion
A SINGLE ELECTRON Orbital magnetic moment
This general result shows that the orbital magnetic moment of a charged particle is proportional to its angular momentum.
In order to develop this idea further, one needs to make use of quantum mechanics.
The stationary states of an electron is characterised by 4 quantum numbers n, , m, and σ.
Remembering that spatial representation cannot take into account all of the subtleties of quantum mechanics!
Classical
Quantum mechanics
Angular momentum
Any direction, any length
Length and projection an one axis can only take discrete, well defined values.
Stern and Gerlach showed experimentally that the electron also has a magnetic moment which has come to be known as spin.
The electron can only have two spin states characterised by σ = ±1/2.
The associated angular momentum is written as:
In a similar way to the orbital magnetic moment, the spin magnetic moment is proportional to the angular momentum.
!!!
Spin magnetic moment
Total magnetic moment is not in general collinear with the total angular momentum.
Remembering that spatial representation cannot take into account all of the subtleties of quantum mechanics!
States of individual electrons or hydrogen like atoms
Stationary states of an electron
,
Operador
For the hydrogen atom,
Solution:
with wave functions
For hydrogen,
,
For other atoms (or ions) depends on the atomic number of the element, and on the number of electrons considered in the central potential.
total wave function:
spin state
MANY ELECTRON ATOMS Hartree's method- The central field approximation: configurations
is the spin-orbit coupling hamiltonian.
Schrodinger's equation for such a system is impossible to solve directly.
re-writing
where,
is a fictitious potential >>
perturbação
,
state of an atom:
amongst the N electrons there is one in a state, another in a state, and so on.
The energy of the atomic state:
Such a state is called a configuration.
The configuration of lowest energy is found by successively filling the individual states of lowest energy
Total orbital and spin angular momenta:
For a full shell:
A full shell is not magnetic, and thus does not carry an intrinsic magnetic moment.
Carbon atom.
Configuration 1s2, 2s2, 2p2
1s2 2s2
2p2
The multiplicity is 15!
A configuration where all of the shells are full is non degenerate!
= 1 0 -1
The interesting cases to consider from the point of view of magnetism are the cases where there are unfilled shells.
Solving...
Example
Terms
partially lifts the degeneracy of each configuration.
Intra-atomic correlations
Leads to energy levels known as "terms".
Each term is characterised by and
the values of the individual spins are those which maximise S, and are compatible with the Pauli exclusion principle.
the values of the individual orbital angular momenta are those which maximize , and are compatible with the first rule and the Pauli exclusion principle.
Example
Carbon atom.
Configuration 1s2, 2s2, 2p2
1s2 2s2
= 1 0 -1
Solving...
2p2
Spin orbit coupling
The origin of this coupling is the following: in the referential of the electron, the motion of the nucleus produces a magnetic field which interacts with the spin magnetic moment.
This perturbation leads to different terms.
is negative for a shell less than half full, and positive for the opposite case.
Multiplets
The degeneracy of each term is partially lifted by the spin-orbit interaction. Each new energy level, known as a "multiplet", is characterised by the quantum number
The ground state multiplet is such that if the shell is more than half full, and when it is less than half full.
Example
At this stage, the further liftings of the degeneracy can only take place as a result of external perturbations such as a magnetic field (Zeeman effect), or the effects of neighbouring atoms when the atom is no longer free, and is part of a solid.
Hydrogen-like atoms
or
Many electron atoms
Points to remember
Points to remember
Hartree’s method
For an iron atom the atomic number is Z = 26, the ground state configuration is written as:
Terms
States of a given term are of the type
Multiplets
Within a multiplet. there exists a basis of 2J + 1 states
Points to remember
magnetism of free ions and atoms
Using
not necessary collinear with
quantum mechanics reveals that within each multiplet the total magnetic moment and the total angular momentum can be considered to be collinear, and linked by the formula:
Points to remember: