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The Pauli exclusion principle is the quantum mechanical principle that no two identical fermions (particles with half-integer spin) may occupy the same quantum state simultaneously. A more rigorous statement is that the total wave function for two identical fermions is anti-symmetric with respect to exchange of the particles. The principle was formulated by Austrian physicist Wolfgang Pauli in 1925.

For example, no two electrons in a single atom can have the same four quantum numbers; if n, l, and ml are the same, ms must be different such that the electrons have opposite spins, and so on.

Integer spin particles, bosons, are not subject to the Pauli exclusion principle: any number of identical bosons can occupy the same quantum state, as with, for instance, photons produced by a laser and Bose-Einstein condensate.

Overview

The three types of particles from which the ordinary atom is made—protons, electrons, and neutrons—are all subject to it, and the structure and chemical behavior of atoms is due to it. It causes atoms to take up the space they do, since electrons cannot all congregate in the lowest-energy state but must occupy higher energy states at a distance from lower-energy electrons, therefore matter made of atoms occupies space rather than being condensed. As such, the Pauli exclusion principle underpins many properties of everyday matter, from its large-scale stability to the periodic table of the elements.

Fermions, particles with antisymmetric wave functions, obey the Pauli exclusion principle. In addition to the electron, proton and neutron, these include neutrinos and quarks (the constituent particles of protons and neutrons), and some atoms such as helium-3. All fermions have "half-integer spin", i.e. their intrinsic angular momentum value is $$\hbar = h/2\pi$$ (reduced Planck's constant) times a half-integer (1/2, 3/2, 5/2, etc.). In the theory of quantum mechanics fermions are described by antisymmetric states. Particles with integer spin (called bosons) have symmetric wave functions; unlike fermions they may share the same quantum states. Bosons include the photon, the Cooper pairs which are responsible for superconductivity, and the W and Z bosons. (Fermions take their name from the Fermi–Dirac statistical distribution that they obey, and bosons from their Bose–Einstein distribution).
History

In the early 20th century it became evident that atoms and molecules with even numbers of electrons are more chemically stable than those with odd numbers of electrons. In the famous 1916 article The Atom and the Molecule by Gilbert N. Lewis, for example, the third of his six postulates of chemical behavior states that the atom tends to hold an even number of electrons in the shell and especially to hold eight electrons which are normally arranged symmetrically at the eight corners of a cube (see: cubical atom). In 1919 chemist Irving Langmuir suggested that the periodic table could be explained if the electrons in an atom were connected or clustered in some manner. Groups of electrons were thought to occupy a set of electron shells about the nucleus.[1] In 1922, Niels Bohr updated his model of the atom by assuming that certain numbers of electrons (for example 2, 8 and 18) corresponded to stable "closed shells".

Pauli looked for an explanation for these numbers, which were at first only empirical. At the same time he was trying to explain experimental results in the Zeeman effect in atomic spectroscopy and in ferromagnetism. He found an essential clue in a 1924 paper by Edmund C. Stoner which pointed out that for a given value of the principal quantum number (n), the number of energy levels of a single electron in the alkali metal spectra in an external magnetic field, where all degenerate energy levels are separated, is equal to the number of electrons in the closed shell of the rare gases for the same value of n. This led Pauli to realize that the complicated numbers of electrons in closed shells can be reduced to the simple rule of one per state, if the electron states are defined using four quantum numbers. For this purpose he introduced a new two-valued quantum number, identified by Samuel Goudsmit and George Uhlenbeck as electron spin.
Connection to quantum state symmetry

The Pauli exclusion principle with a single-valued many-particle wavefunction is equivalent to requiring the wavefunction to be antisymmetric. An antisymmetric two-particle state is represented as a sum of states in which one particle is in state \scriptstyle |x \rangle and the other in state $$\scriptstyle |y\rangle$$:

$$|\psi\rangle = \sum_{x,y} A(x,y) |x,y\rangle$$

and antisymmetry under exchange means that A(x,y) = -A(y,x). This implies that A(x,x)=0, which is Pauli exclusion. It is true in any basis, since unitary changes of basis keep antisymmetric matrices antisymmetric, although strictly speaking, the quantity A(x,y) is not a matrix but an antisymmetric rank-two tensor.

Conversely, if the diagonal quantities A(x,x) are zero in every basis, then the wavefunction component:

$$A(x,y)=\langle \psi|x,y\rangle = \langle \psi | ( |x\rangle \otimes |y\rangle ) is necessarily antisymmetric. To prove it, consider the matrix element: \( \langle\psi| ((|x\rangle + |y\rangle)\otimes(|x\rangle + |y\rangle)) \,$$

This is zero, because the two particles have zero probability to both be in the superposition state $$\scriptstyle |x\rangle + |y\rangle$$. But this is equal to

$$\langle \psi |x,x\rangle + \langle \psi |x,y\rangle + \langle \psi |y,x\rangle + \langle \psi | y,y \rangle \,$$

The first and last terms on the right hand side are diagonal elements and are zero, and the whole sum is equal to zero. So the wavefunction matrix elements obey:

$$\langle \psi|x,y\rangle + \langle\psi |y,x\rangle = 0 \,.$$

or

$$A(x,y)=-A(y,x) \,$$

Pauli principle in advanced quantum theory

According to the spin-statistics theorem, particles with integer spin occupy symmetric quantum states, and particles with half-integer spin occupy antisymmetric states; furthermore, only integer or half-integer values of spin are allowed by the principles of quantum mechanics. In relativistic quantum field theory, the Pauli principle follows from applying a rotation operator in imaginary time to particles of half-integer spin. Since, nonrelativistically, particles can have any statistics and any spin, there is no way to prove a spin-statistics theorem in nonrelativistic quantum mechanics.

In one dimension, bosons, as well as fermions, can obey the exclusion principle. A one-dimensional Bose gas with delta function repulsive interactions of infinite strength is equivalent to a gas of free fermions. The reason for this is that, in one dimension, exchange of particles requires that they pass through each other; for infinitely strong repulsion this cannot happen. This model is described by a quantum nonlinear Schrödinger equation. In momentum space the exclusion principle is valid also for finite repulsion in a Bose gas with delta function interactions,[2] as well as for interacting spins and Hubbard model in one dimension, and for other models solvable by Bethe ansatz. The ground state in models solvable by Bethe ansatz is a Fermi sphere.
Consequences
Atoms and the Pauli principle

The Pauli exclusion principle helps explain a wide variety of physical phenomena. One particularly important consequence of the principle is the elaborate electron shell structure of atoms and the way atoms share electrons, explaining the variety of chemical elements and their chemical combinations. An electrically neutral atom contains bound electrons equal in number to the protons in the nucleus. Electrons, being fermions, cannot occupy the same quantum state, so electrons have to "stack" within an atom, i.e. have different spins while at the same place.

An example is the neutral helium atom, which has two bound electrons, both of which can occupy the lowest-energy (1s) states by acquiring opposite spin; as spin is part of the quantum state of the electron, the two electrons are in different quantum states and do not violate the Pauli principle. However, the spin can take only two different values (eigenvalues). In a lithium atom, with three bound electrons, the third electron cannot reside in a 1s state, and must occupy one of the higher-energy 2s states instead. Similarly, successively larger elements must have shells of successively higher energy. The chemical properties of an element largely depend on the number of electrons in the outermost shell; atoms with different numbers of shells but the same number of electrons in the outermost shell have similar properties, which gives rise to the periodic table of the elements.
Solid state properties and the Pauli principle

In conductors and semi-conductors, free electrons have to share entire bulk space. Thus, their energy levels stack up, creating band structure out of each atomic energy level. In strong conductors (metals) electrons are so degenerate that they can not even contribute much to the thermal capacity of a metal. Many mechanical, electrical, magnetic, optical and chemical properties of solids are the direct consequence of Pauli exclusion.
Stability of matter

The stability of the electrons in an atom itself is not related to the exclusion principle, but is described by the quantum theory of the atom. The underlying idea is that close approach of an electron to the nucleus of the atom necessarily increases its kinetic energy, an application of the uncertainty principle of Heisenberg.[3] However, stability of large systems with many electrons and many nuclei is a different matter, and requires the Pauli exclusion principle.[4]

It has been shown that the Pauli exclusion principle is responsible for the fact that ordinary bulk matter is stable and occupies volume. This suggestion was first made in 1931 by Paul Ehrenfest, who pointed out that the electrons of each atom cannot all fall into the lowest-energy orbital and must occupy successively larger shells. Atoms therefore occupy a volume and cannot be squeezed too closely together.[5]

A more rigorous proof was provided in 1967 by Freeman Dyson and Andrew Lenard, who considered the balance of attractive (electron-nuclear) and repulsive (electron-electron and nuclear-nuclear) forces and showed that ordinary matter would collapse and occupy a much smaller volume without the Pauli principle.[6] The consequence of the Pauli principle here is that electrons of the same spin are kept apart by a repulsive exchange interaction, which is a short-range effect, acting simultaneously with the long-range electrostatic or coulombic force. This effect is partly responsible for the everyday observation in the macroscopic world that two solid objects cannot be in the same place in the same time.
Astrophysics and the Pauli principle

Dyson and Lenard did not consider the extreme magnetic or gravitational forces which occur in some astronomical objects. In 1995 Elliott Lieb and coworkers showed that the Pauli principle still leads to stability in intense magnetic fields such as in neutron stars, although at a much higher density than in ordinary matter.[7] It is a consequence of general relativity that, in sufficiently intense gravitational fields, matter collapses to form a black hole.

Astronomy provides a spectacular demonstration of the effect of the Pauli principle, in the form of white dwarf and neutron stars. In both types of body, atomic structure is disrupted by large gravitational forces, leaving the constituents supported by "degeneracy pressure" alone. This exotic form of matter is known as degenerate matter. In white dwarfs atoms are held apart by electron degeneracy pressure. In neutron stars, subject to even stronger gravitational forces, electrons have merged with protons to form neutrons. Neutrons are capable of producing an even higher degeneracy pressure, albeit over a shorter range. This can stabilize neutron stars from further collapse, but at a smaller size and higher density than a white dwarf. Neutrons are the most "rigid" objects known; their Young modulus (or more accurately, bulk modulus) is 20 orders of magnitude larger than that of diamond. However, even this enormous rigidity can be overcome by the gravitational field of a massive star or by the pressure of a supernova, leading to the formation of a black hole.

Exchange force
Exchange interaction
Exchange symmetry
Hund's rule
Fermi hole

References

^ Langmuir, Irving (1919). "The Arrangement of Electrons in Atoms and Molecules" (– Scholar search). Journal of the American Chemical Society 41 (6): 868–934. doi:10.1021/ja02227a002. Retrieved 2008-09-01.[dead link][dead link]
^ A. Izergin and V. Korepin, Letter in Mathematical Physics vol 6, page 283, 1982
^ Elliot J. Lieb The Stability of Matter and Quantum Electrodynamics
^ This realization is attributed by Lieb and by GL Sewell (2002). Quantum Mechanics and Its Emergent Macrophysics. Princeton University Press. ISBN 0691058326. to FJ Dyson and A Lenard: Stability of Matter, Parts I and II (J. Math. Phys., 8, 423-434 (1967); J. Math. Phys., 9, 698-711 (1968) ).
^ As described by FJ Dyson (J.Math.Phys. 8, 1538-1545 (1967) ), Ehrenfest made this suggestion in his address on the occasion of the award of the Lorentz Medal to Pauli.
^ FJ Dyson and A Lenard: Stability of Matter, Parts I and II (J. Math. Phys., 8, 423-434 (1967); J. Math. Phys., 9, 698-711 (1968) ); FJ Dyson: Ground-State Energy of a Finite System of Charged Particles (J.Math.Phys. 8, 1538-1545 (1967) )
^ E.H. Lieb, M. Loss and J.P. Solovej, Phys. Rev. Letters, 75, 985-9 (1995) "Stability of Matter in Magnetic Fields"

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