This document provides an introduction to the Heisenberg model of magnetism. It discusses how the exchange interaction leads to a dependence of the energy of a system on the total spin, even when the electric interaction is spin-independent. For a system of two electrons, the energy depends on whether the total spin is a singlet (total spin = 0) or triplet (total spin = 1). This energy difference can be modeled by an effective Hamiltonian containing an exchange term. The discussion is then generalized to many-electron systems via the Heisenberg Hamiltonian. The document also covers superexchange, RKKY interaction, and double exchange as mechanisms for indirect exchange interactions in solids.
Attosecond pulses produced by using HHG in gases, it is possible to make a few simple statements: attosecond pulses are unique tools for the investigation of ultrafast electronic processes in atoms, molecules, nano structures and solids. Impressive progress has been demonstrated from the technological point of view, with the possibility to routinely generate attosecond pulses in perfectly reproducible ways.
Hello, I am Subhajit Pramanick. I and my classmate, Anannya Sahaw, both presented this ppt in seminar of our Institute, Indian Institute of Technology, Kharagpur. The topic of this presentation is on exchange interaction and their consequences. It includes the basic of exchange interaction, the origin of it, classification of it and their discussions etc. We hope you will all enjoy by reading this presentation. Thank you.
more chemistry contents are available
1. pdf file on Termmate: https://www.termmate.com/rabia.aziz
2. YouTube: https://www.youtube.com/channel/UCKxWnNdskGHnZFS0h1QRTEA
3. Facebook: https://web.facebook.com/Chemist.Rabia.Aziz/
4. Blogger: https://chemistry-academy.blogspot.com/
BS-III
Lecture 8: Introduction to Quantum Chemical Simulation graduate course taught at MIT in Fall 2014 by Heather Kulik. This course covers: wavefunction theory, density functional theory, force fields and molecular dynamics and sampling.
Attosecond pulses produced by using HHG in gases, it is possible to make a few simple statements: attosecond pulses are unique tools for the investigation of ultrafast electronic processes in atoms, molecules, nano structures and solids. Impressive progress has been demonstrated from the technological point of view, with the possibility to routinely generate attosecond pulses in perfectly reproducible ways.
Hello, I am Subhajit Pramanick. I and my classmate, Anannya Sahaw, both presented this ppt in seminar of our Institute, Indian Institute of Technology, Kharagpur. The topic of this presentation is on exchange interaction and their consequences. It includes the basic of exchange interaction, the origin of it, classification of it and their discussions etc. We hope you will all enjoy by reading this presentation. Thank you.
more chemistry contents are available
1. pdf file on Termmate: https://www.termmate.com/rabia.aziz
2. YouTube: https://www.youtube.com/channel/UCKxWnNdskGHnZFS0h1QRTEA
3. Facebook: https://web.facebook.com/Chemist.Rabia.Aziz/
4. Blogger: https://chemistry-academy.blogspot.com/
BS-III
Lecture 8: Introduction to Quantum Chemical Simulation graduate course taught at MIT in Fall 2014 by Heather Kulik. This course covers: wavefunction theory, density functional theory, force fields and molecular dynamics and sampling.
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origin of quantum physics -
Inadequacy of classical mechanics and birth of QUANTUM PHYSICS
ref: Quantum mechanics: concepts and applications, N. Zettili
Magnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materialsMagnetic properties of materials
origin of quantum physics -
Inadequacy of classical mechanics and birth of QUANTUM PHYSICS
ref: Quantum mechanics: concepts and applications, N. Zettili
On the basis of the first law of thermodynamics, an analysis of the orientation of structural interactions was carried out. In the systems in which the interaction proceeds along the potential gradient (positive work), the resultant potential energy is found based on the principle of adding reciprocals of corresponding energies of subsystems - there is a corpuscular mechanism. In the systems in which the interactions proceed against the potential gradient (negative performance) the algebraic addition of their masses, as well as the corresponding energies of subsystems is performed - there is a wave mechanism. Act of quantum action expressed via Plank’s constant is narrowed to the energy equilibrium-exchange redistribution between the corpuscular and wave processes, that is demonstrated via the angular vector of such motion. Еnergy characteristics of functional states of bio-systems are defined basically by P-parameter values of atom first valence electron. The principles of stationary biosystem formation are similar to the conditions of wave processes in the phase. Under the condition of the minimum of such interactions, the pathological (but not stationary) biostructures containing the molecular hydrogen can be formed.
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Heavy metals are naturally occuring metallic chemical elements that have relatively high density, and are toxic at even low concentrations. All toxic metals are termed as heavy metals irrespective of their atomic mass and density, eg. arsenic, lead, mercury, cadmium, thallium, chromium, etc.
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Richard's aventures in two entangled wonderlandsRichard Gill
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2. Most important reference followed
in this lecture
Magnetism in Condensed Matter Physics
Stephen Blundell
Oxford Master Series in Condensed Matter Physics
3. Exchange interactions
If relativistic effects are not considered, then
the electric interaction between particles does not depend on their spins
In the absence of a magnetic field, the Hamiltonian of a system of particles
in electric interaction does not contain spin operators
4. A look to the hamiltonian:
a difficult interacting many-body system.
Kinetic energy operator for the electrons
Potential acting on the electrons
due to the nuclei
Electron-electron interaction
Kinetic energy operator for the nuclei
Nucleus-nucleus interaction
5. Exchange interactions
If relativistic effects are not considered, then
the electric interaction between particles does not depend on their spins
In the absence of a magnetic field, the Hamiltonian of a system of particles
in electric interaction does not contain spin operators
When it is applied to a wavefunction, it does not affect the spinoidal variables
The wave function of a system of particles can be written as a product
It depends only on the
spatial coordinates of the
particles
It depends only on the spin
variables
The Schrödinger equation determines only , leaving arbitrary
6. The indistinguisibility of the particles leads to
symmetry conditions on the wave function
Despite the fact that the electric interaction is spin-independent, there is a
dependendency of the energy of the system with respect the total spin
Let us consider a system of two identical particles.
After solving the Schrödinger equation, we find a set of energy levels, each of
which are associated with a spatial wavefunction
Since the particles are identical, the Hamiltonian of the system has to be invariant
with respect the permutation of the particles
has to be symmetric or antisymmetric
7. The possible values of the energy of a system of
identical particles depend on the total spin system
Let us assume now that the particles have spin 1/2
The total wave function (product of a spatial coordinate wave function
and the spinorial wave function) has to be antisymmetric with respect the
permutation of the two particles
symmetric antisymmetric Total spin = 0
(spins aligned
antiparallel one
to the other)
antisymmetric symmetric Total spin = 1
(spins aligned
parallel one to
the other)
The energy only depends on , that is determined by the total spin
8. The possible values of the energy of a system of
identical particles depend on the total spin system
Let us assume now that the particles have spin 1/2
Consider two electrons which have spatial coordinates and
Let us assume that the two particles, without considering
their mutual interaction, are in states that can be
represented by single electron coordinate wavefunctions
and
The overall wave function of the system for a state with total spin
Triplet ( )
Singlet ( )
9. The possible values of the energy of a system of
identical particles depend on the total spin system
The energies of the two possible states are
The overall wave function of the system for a state with total spin
Triplet ( )
Singlet ( )
We assume that the spin
part of the wave function
is normalized
10. Mean value of the energy in the
singlet and triplet states
The energies of the single state is
We assume that the spin
part of the wave function
is normalized
11. Mean value of the energy in the
singlet and triplet states
The energies of the triplet state is
We assume that the spin
part of the wave function
is normalized
12. Mean value of the energy in the
singlet and triplet states
The difference in energies between the singlet and the triplet state is
(to obtain this expression remembers that the Hamiltonian operator is self-adjoint)
The difference between single and triplet states can be parametrized by
13. Explanation of this mapping:
The coupling of two spins
Consider two spin-1/2 particles coupled by an interaction given by the Hamiltonian
Operator for the spin of particle a Operator for the spin of particle b
Considered as a joint entity, the total spin can be represented by the operator
so that
14. The coupling of two spins:
eigenvalue of different operators
The eigenvalue of is The eigenvalue of and
are 3/4
Combining two spin-1/2 particles results in a joint entity with spin quantum number
Since Since
15. The coupling of two spins:
eigenstates of different operators
Let us consider the following basis
First arrow: z-component of the spin labelled as a
Second arrow: z-component of the spin labelled as b
The eigenstates of are linear combination of these basis states
The degeneracy of each state of each state is given by
Singlet
Triplet
16. The coupling of two spins:
eigenstates of different operators
Let us consider the following basis
First arrow: z-component of the spin labelled as a
Second arrow: z-component of the spin labelled as b
The eigenstates of are linear combination of these basis states
The z component of the spin of the state,
Is the sum of the z components of the individual spins
Singlet
Triplet
Because eigenstates are mixtures of states in the original basis, it is not
possible in general to know both the z-component of the original spins
and the total spin of the resultant entity
17. The coupling of two spins:
Summary
A assumed to be positive
in the diagram
18. Mean value of the energy in the
singlet and triplet states
The difference in energies between the singlet and the triplet state is
(to obtain this expression remembers that the Hamiltonian operator is self-adjoint)
The difference between single and triplet states can be parametrized by
For a singlet state For a triplet state
The Hamiltonian can be written in the form of an effective Hamiltonian
19. Effective Hamiltonian to describe
singlet and triplet states
The Hamiltonian can be written in the form of an effective Hamiltonian
Constant term:
Can be absorbed into other
constant energy-terms
Spin-dependent term:
Since
We can define the exchange constant (or exchange integral) as
And hence, the spin dependent term in the model Hamiltonian can be written as
20. Effective Hamiltonian to describe
singlet and triplet states
And hence, the spin dependent term in the model Hamiltonian can be written as
21. Generalization for more than
two electrons
The spin dependent term in the model Hamiltonian can be written as
Generalizing to a many-body system is far from trivial
Since the early days of Quantum Mechanics, it was recognized that interactions
such as the previous one probably apply between all neighboring atoms
This motivates the Hamiltonian of the Heisenberg model
The factor of 2 is omitted because the
summation includes each pair of spins twice
The factor of 2 appears because the
summation on i >j avoids the double counting
22. General features respect the (complicate)
calculation of exchange integrals
If the two electrons are on the same atom the exchange integral is usually positive
Antisymmetric spatial state
Minimizes the Coulomb repulsion between the two electrons by keeping them
apart
Good agreement with Hund’s first rule
23. General features respect the (complicate)
calculation of exchange integrals
If the two electrons are on neighboring atoms
Any joint state will be a combination of a state centered on one atom and a state
centered on the other
Antisymmetric state usually more
energetic
(more curvature that implies larger
kinetic energy),
and the system tends to be in the
bonding state
The correct states to consider are molecular orbitals that can be:
- Bonding (spatially symmetric) (asymmetric spin state)
- Antibonding (spatially asymmetric) (symmetric spin state)
25. Direct exchange
If the electrons in neighboring magnetic atoms interact via an exchange
interaction, this is known as direct exchange
The exchange interaction proceeds directly without the need for an intermediary.
• 4f electrons in rare earths are strongly localized
• 3d transition metals, extremely difficult to justify magnetic properties from
direct exchange. Some of these materials (Fe, Co, Ni) are metals, and
conduction (delocalized) electrons should not ne neglected.
Physical situation is rarely that simple:
Very often, direct exchange cannot be an important mechanism in controlling the
magnetic properties because there is insufficient direct orbital between
neighboring magnetic orbitals
26. Indirect exchange in ionic solids:
superexchange
Superexchange is defined as an indirect exchange interaction between
non-neighboring magnetic ions which is mediated by a non-magnetic ion
which is placed in between the magnetic ion
Imagine two transition metal ions
separated by an oxygen atom
(for instance Mn2+ manganese ions
connected via O2- oxygen ions in MgO)
For simplicity, we assume that the magnetic
moment on the transition metal ion is due
to a single unpaired electron
In the perfectly ionic picture, each metal ion
would have a single unpaired electron in a
d-orbital and the oxygen would have two
p-electrons in its outermost occupied state
27. Indirect exchange in ionic solids:
superexchange
Superexchange is defined as an indirect exchange interaction between
non-neighboring magnetic ions which is mediated by a non-magnetic ion
which is placed in between the magnetic ion
In the perfectly ionic picture, each metal ion would have a single unpaired
electron in a d-orbital and the oxygen would have two p-electrons in its
outermost occupied state
In the antiferromagnetic configuration, two
electrons with spin up and two electrons with
spin down
The ground state configuration is (a)
But the excited states (b) and (c) are also possible
Therefore (a) can mix with the excited states (b) and (c)
and the magnetic electrons can be delocalized over
the M-O-M unit, lowering the kinetic energy
28. Indirect exchange in ionic solids:
superexchange
Superexchange is defined as an indirect exchange interaction between
non-neighboring magnetic ions which is mediated by a non-magnetic ion
which is placed in between the magnetic ion
In the perfectly ionic picture, each metal ion would have a single unpaired
electron in a d-orbital and the oxygen would have two p-electrons in its
outermost occupied state
In the ferromagnetic configuration, three
electrons with spin up and one electron with spin
down
The ground state configuration is (a)
The excited states (b) and (c) are not possible due
to exclusion principle
Therefore (a) cannot mix with the excited states (b) and (c).
The ferromagnetic state is more localized and costs more energy.
29. Indirect exchange in ionic solids:
superexchange
Superexchange is a second order process and is derived from second
order perturbation theory
The energy involved is:
Directly proportional to the square of
the matrix element of the transition
Related with the width of the
conduction band in a simple tight-
binding approach
Inversely proportional to the to the
energy cost of making the transition
state
Related with the Coulomb energy
30. Indirect exchange in ionic solids:
superexchange
The exchange integral consists of two parts
Potential exchange term
Represents the electron repulsion.
Favours ferromagnetic state.
Small when the atoms are well separated
Kinetic exchange term
Favours delocalization of the electrons.
Dominates when the atoms are well
separated.
Strongly dependent upon the angle of the
M-O-M bond.
31. Indirect exchange in metals:
RKKY interaction
In metals, the exchange interaction between magnetic ions can be
mediated by the conduction electrons
A localized magnetic moment spin polarizes the conduction electrons
The magnetic interaction is indirect because it does not involve direct
coupling between magnetic moments.
This polarization, in turn, couples to a neighbouring localized magnetic
moment a distance away
Ruderman, Kittel, Kasuya and
Yoshida interaction
• The interaction is long range
• It might be ferro or antiferro
depending on the distance
• Oscillatory coupling, with wave
length because sharpness
of Fermi surface
32. Double exchange
A ferromagnetic exchange interaction which occurs because the
magnetic ion can show mixed valency, i.e. that it can exist in more than
one oxidation state
Examples: compounds containing the Mn ion which can exist in
oxidation state 3 or 4 (Mn3+ or Mn4+)
La1-xSrxMnO3
Sr is divalent (Sr+2) a fraction x of the Mn ions are Mn4+
La is trivalent (La+3) a fraction (1-x) of the Mn ions are Mn3+
The end members of the series are both antiferromagnetic insulators (as
expected for an oxide material in which magnetism is mediated by
superexchange through the oxygen
When LaMnO3 is doped with Sr up to x = 0.175, the Jahn-Teller distortion
vanishes and the system becomes ferromagnetic with a Curie temperature
around room temperature, below which the system is metallic
33. Double exchange
A ferromagnetic exchange interaction which occurs because the
magnetic ion can show mixed valency, i.e. that it can exist in more than
one oxidation state
La1-xSrxMnO3
The eg electron of a Mn3+ ion can hop to
the neighboring site only if there is a
vacancy there with the same spin
(hopping proceeds without spin flip of the
hopping electron)
If the neighboring atom is a Mn4+
(no electrons in its eg shell),
this should present no problem
However, there is a strong single-center
exchange interaction between the eg
electron and the t2g level, which wants to
keep them all aligned
Ferromagnetic alignement of neighboring
ions is therefore required to maintain the
high-spin alignment on the donating and
receiving ion
34. The Pauli spin matrices
Any two by two matrix can be written in terms of them
(they are a basis of the Hilbert space of the (2×2)
matrices
Any matrix that can be written has four numbers in it
It can be written as a linear combination of four matrices
One special way of doing this is to choose the Pauli spin matrices as the basis
Are complex
numbers
36. Pauli spin matrices as components
of a vector of matrices
You can use in different coordinate systems as though it is a vector
37. Definition of the spin angular
momentum operator
We define the spin angular momentum operator by
Or, in components
We are using the convention that the angular
momentum is measured in units of
The angular momentum associated with an electron is
38. Definition of the spin angular
momentum operator
We define the spin angular momentum operator by
Or, in components
Only the operator is diagonal.
If the electron spin points along the representation is particularly simple
39. Representation of the spin operator
along -direction
Eigenstates of Eigenvalues of
Spin pointing parallel
to the -axis
Spin pointing antiparallel
to the -axis
40. axis
Eigenstates corresponding to the spin pointing
parallel or antiparallel to the and axis
axis
All of them have the same magnitude of the eigenvalue: ½
positive if pointing parallel to the axis
negative if pointing antiparallel
These eigenstates are normalized
41. Spinor representation: the two-component
representation of the spin wave function
Where and are complex numbers and it is conventional to normalize the state
42. Total spin angular momentum operator
The spin square operator is given by
Since the eigenvalues of are always
So we have the result that for any spin state,
43. Commutation relations between the spin operators
From the commutation relations of the Pauli matrices, it follows immediatly than
And cyclic permutations thereof.
Besides, each of these components commute with
Thus, it is possible to know simultaneously the total spin and one of the
components, but it is impossible to know more than one component
simultaneously
44. Raising and lowering operator
Raising operator Lowering operator
They are not Hermitian operators (not observables)
45. Raising and lowering operator effect on spin states
The raising operator will raise the
component of the spin angular
momentum by
The lowering operator will lower the
component of the spin angular
momentum by
If the component of the spin angular momentum is already at its maximum
(minimum) level, the raising (lowering) operator will annihilate the state