Pauli exclusion principle

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Wolfgang Pauli formulated the law stating that no two electrons can have the same set of quantum numbers. Wolfgang Pauli young.jpg
Wolfgang Pauli formulated the law stating that no two electrons can have the same set of quantum numbers.

The Pauli exclusion principle is the quantum mechanical principle which states that two or more identical fermions (particles with half-integer spin) cannot occupy the same quantum state within a quantum system simultaneously. This principle was formulated by Austrian physicist Wolfgang Pauli in 1925 for electrons, and later extended to all fermions with his spin–statistics theorem of 1940.


In the case of electrons in atoms, it can be stated as follows: it is impossible for two electrons of a poly-electron atom to have the same values of the four quantum numbers: n, the principal quantum number; , the azimuthal quantum number; m, the magnetic quantum number; and ms, the spin quantum number. For example, if two electrons reside in the same orbital, then their n, , and m values are the same; therefore their ms must be different, and thus the electrons must have opposite half-integer spin projections of 1/2 and −1/2.

Particles with an integer spin, or 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 or atoms in a Bose–Einstein condensate.

A more rigorous statement is that, concerning the exchange of two identical particles, the total (many-particle) wave function is antisymmetric for fermions, and symmetric for bosons. This means that if the space and spin coordinates of two identical particles are interchanged, then the total wave function changes its sign for fermions and does not change for bosons.

If two fermions were in the same state (for example the same orbital with the same spin in the same atom), interchanging them would change nothing and the total wave function would be unchanged. The only way the total wave function can both change sign as required for fermions and also remain unchanged is that this function must be zero everywhere, which means that the state cannot exist. This reasoning does not apply to bosons because the sign does not change.


The Pauli exclusion principle describes the behavior of all fermions (particles with "half-integer spin"), while bosons (particles with "integer spin") are subject to other principles. Fermions include elementary particles such as quarks, electrons and neutrinos. Additionally, baryons such as protons and neutrons (subatomic particles composed from three quarks) and some atoms (such as helium-3) are fermions, and are therefore described by the Pauli exclusion principle as well. Atoms can have different overall "spin", which determines whether they are fermions or bosons — for example helium-3 has spin 1/2 and is therefore a fermion, in contrast to helium-4 which has spin 0 and is a boson. [1] :123–125 As such, the Pauli exclusion principle underpins many properties of everyday matter, from its large-scale stability, to the chemical behavior of atoms.

"Half-integer spin" means that the intrinsic angular momentum value of fermions is (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. In contrast, 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.)


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 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 any given shell, and especially to hold eight electrons, thought to be typically arranged symmetrically at the eight corners of a cube. [2] 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 around the nucleus. [3] 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". [4] :203

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 of 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 noble 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 electron 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. [5] [6]

Connection to quantum state symmetry

In his Nobel lecture, Pauli clarified the important of quantum state symmetry to the exclusion principle: [7]

Among the different classes of symmetry, the most important ones (which moreover for two particles are the only ones) are the symmetrical class, in which the wave function does not change its value when the space and spin coordinates of two particles are permuted, and the antisymmetrical class, in which for such a permutation the wave function changes its sign...[The antisymmetrical class is] the correct and general wave mechanical formulation of the exclusion principle.

The Pauli exclusion principle with a single-valued many-particle wavefunction is equivalent to requiring the wavefunction to be antisymmetric with respect to exchange. If and range over the basis vectors of the Hilbert space describing a one-particle system, then the tensor product produces the basis vectors of the Hilbert space describing a system of two such particles. Any two-particle state can be represented as a superposition (i.e. sum) of these basis vectors:

where each A(x,y) is a (complex) scalar coefficient. Antisymmetry under exchange means that A(x,y) = −A(y,x). This implies A(x,y) = 0 when x = y, which is Pauli exclusion. It is true in any basis since local changes of basis keep antisymmetric matrices antisymmetric.

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

is necessarily antisymmetric. To prove it, consider the matrix element

This is zero, because the two particles have zero probability to both be in the superposition state . But this is equal to

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


For a system with n > 2 particles, the multi-particle basis states become n-fold tensor products of one-particle basis states, and the coefficients of the wavefunction are identified by n one-particle states. The condition of antisymmetry states that the coefficients must flip sign whenever any two states are exchanged: for any . The exclusion principle is the consequence that, if for any then This shows that none of the n particles may be in the same state.

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.

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, the 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, [8] 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.



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 as other electrons, so electrons have to "stack" within an atom, i.e. have different spins while at the same electron orbital as described below.

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 occupied electron shells but the same number of electrons in the outermost shell have similar properties, which gives rise to the periodic table of the elements. [9] :214–218

To test the Pauli exclusion principle for the He atom, Gordon Drake [10] carried out very precise calculations for hypothetical states of the He atom that violate it, which are called paronic states. Later, K. Deilamian et al. [11] used an atomic beam spectrometer to search for the paronic state 1s2s 1S0 calculated by Drake. The search was unsuccessful and showed that the statistical weight of this paronic state has an upper limit of 5x10−6. (The exclusion principle implies a weight of zero.)

Solid state properties

In conductors and semiconductors, there are very large numbers of molecular orbitals which effectively form a continuous band structure of energy levels. In strong conductors (metals) electrons are so degenerate that they cannot even contribute much to the thermal capacity of a metal. [12] :133–147 Many mechanical, electrical, magnetic, optical and chemical properties of solids are the direct consequence of Pauli exclusion.

Stability of matter

The stability of each electron state in an atom is described by the quantum theory of the atom, which shows that close approach of an electron to the nucleus necessarily increases the electron's kinetic energy, an application of the uncertainty principle of Heisenberg. [13] However, stability of large systems with many electrons and many nucleons is a different question, and requires the Pauli exclusion principle. [14]

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. [15]

A more rigorous proof was provided in 1967 by Freeman Dyson and Andrew Lenard (de), 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. [16] [17]

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 at the same time.


Dyson and Lenard did not consider the extreme magnetic or gravitational forces that 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. [18] 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 bodies, the atomic structure is disrupted by extreme pressure, but the stars are held in hydrostatic equilibrium by degeneracy pressure , also known as Fermi pressure. This exotic form of matter is known as degenerate matter. The immense gravitational force of a star's mass is normally held in equilibrium by thermal pressure caused by heat produced in thermonuclear fusion in the star's core. In white dwarfs, which do not undergo nuclear fusion, an opposing force to gravity is provided 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, neutron 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. Neutron stars 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 neutron star mass exceeding the Tolman–Oppenheimer–Volkoff limit, leading to the formation of a black hole. [19] :286–287

See also

Related Research Articles

Antiparticle Small localized object; a rare type of matter

In particle physics, every type of particle is associated with an antiparticle with the same mass but with opposite physical charges. For example, the antiparticle of the electron is the antielectron. While the electron has a negative electric charge, the positron has a positive electric charge, and is produced naturally in certain types of radioactive decay. The opposite is also true: the antiparticle of the positron is the electron.

Fermion One of two classes of elementary particles

In particle physics, a fermion is a particle that follows Fermi–Dirac statistics and generally has half odd integer spin: spin 1/2, spin 3/2, etc. These particles obey the Pauli exclusion principle. Fermions include all quarks and leptons, as well as all composite particles made of an odd number of these, such as all baryons and many atoms and nuclei. Fermions differ from bosons, which obey Bose–Einstein statistics.

In quantum mechanics, identical particles are particles that cannot be distinguished from one another, even in principle. Species of identical particles include, but are not limited to, elementary particles, composite subatomic particles, as well as atoms and molecules. Quasiparticles also behave in this way. Although all known indistinguishable particles only exist at the quantum scale, there is no exhaustive list of all possible sorts of particles nor a clear-cut limit of applicability, as explored in quantum statistics.

Wave function Mathematical description of the quantum state of a system

A wave function in quantum physics is a mathematical description of the quantum state of an isolated quantum system. The wave function is a complex-valued probability amplitude, and the probabilities for the possible results of measurements made on the system can be derived from it. The most common symbols for a wave function are the Greek letters ψ and Ψ.

The Fock space is an algebraic construction used in quantum mechanics to construct the quantum states space of a variable or unknown number of identical particles from a single particle Hilbert space H. It is named after V. A. Fock who first introduced it in his 1932 paper "Konfigurationsraum und zweite Quantelung".

In quantum mechanics, a Fock state or number state is a quantum state that is an element of a Fock space with a well-defined number of particles. These states are named after the Soviet physicist Vladimir Fock. Fock states play an important role in the second quantization formulation of quantum mechanics.

In quantum mechanics, the spin–statistics theorem relates the intrinsic spin of a particle to the particle statistics it obeys. In units of the reduced Planck constant ħ, all particles that move in 3 dimensions have either integer spin or half-integer spin.

In physics, an anyon is a type of quasiparticle that occurs only in two-dimensional systems, with properties much less restricted than the two kinds of standard elementary particles, fermions and bosons. In general, the operation of exchanging two identical particles, although it may cause a global phase shift, cannot affect observables. Anyons are generally classified as abelian or non-abelian. Abelian anyons play a major role in the fractional quantum Hall effect. Non-abelian anyons have not been definitively detected, although this is an active area of research.

Second quantization Formulation of the quantum many-body problem

Second quantization, also referred to as occupation number representation, is a formalism used to describe and analyze quantum many-body systems. In quantum field theory, it is known as canonical quantization, in which the fields are thought of as field operators, in a manner similar to how the physical quantities are thought of as operators in first quantization. The key ideas of this method were introduced in 1927 by Paul Dirac, and were developed, most notably, by Vladimir Fock and Pascual Jordan later.

In quantum mechanics, a Slater determinant is an expression that describes the wave function of a multi-fermionic system. It satisfies anti-symmetry requirements, and consequently the Pauli principle, by changing sign upon exchange of two electrons. Only a small subset of all possible fermionic wave functions can be written as a single Slater determinant, but those form an important and useful subset because of their simplicity.

Fermis interaction Mechanism of beta decay proposed in 1933

In particle physics, Fermi's interaction is an explanation of the beta decay, proposed by Enrico Fermi in 1933. The theory posits four fermions directly interacting with one another. This interaction explains beta decay of a neutron by direct coupling of a neutron with an electron, a neutrino and a proton.

In quantum field theory, a fermionic field is a quantum field whose quanta are fermions; that is, they obey Fermi–Dirac statistics. Fermionic fields obey canonical anticommutation relations rather than the canonical commutation relations of bosonic fields.

Spin-½ Type of matter

In quantum mechanics, spin is an intrinsic property of all elementary particles. All known fermions, the particles that constitute ordinary matter, have a spin of 1/2. The spin number describes how many symmetrical facets a particle has in one full rotation; a spin of 1/2 means that the particle must be rotated by two full turns before it has the same configuration as when it started.

In chemistry and physics, the exchange interaction is a quantum mechanical effect that only occurs between identical particles. Despite sometimes being called an exchange force in an analogy to classical force, it is not a true force as it lacks a force carrier.

Fermi heap and Fermi hole refer to two closely related quantum phenomena that occur in many-electron atoms. They arise due to the Pauli exclusion principle, according to which no two electrons can be in the same quantum state in a system. Due to indistinguishability of elementary particles, the probability of a measurement yielding a certain eigenvalue must be invariant when electrons are exchanged, which means that the probability amplitude must either remain the same or change sign. For instance, consider an excited state of the helium atom in which electron 1 is in the 1s orbital and electron 2 has been excited to the 2s orbital. It is not possible, even in principle, to distinguish electron 1 from electron 2. In other words, electron 2 might be in the 1s orbital with electron 1 in the 2s orbital. As they are fermions, electrons must be described by an anti-symmetric wavefunction which must change sign under electron exchange, resulting in either a Fermi hole or a Fermi heap. Since electrons repel one another electrically, Fermi holes and Fermi heaps have drastic effects on the energy of many-electron atoms, although the effect can be illustrated in the case of the helium atom.

In quantum mechanics, a raising or lowering operator is an operator that increases or decreases the eigenvalue of another operator. In quantum mechanics, the raising operator is sometimes called the creation operator, and the lowering operator the annihilation operator. Well-known applications of ladder operators in quantum mechanics are in the formalisms of the quantum harmonic oscillator and angular momentum.

Spin is an intrinsic form of angular momentum carried by elementary particles, composite particles (hadrons), and atomic nuclei.

This is a glossary for the terminology often encountered in undergraduate quantum mechanics courses.

Symmetry in quantum mechanics Properties underlying modern physics

Symmetries in quantum mechanics describe features of spacetime and particles which are unchanged under some transformation, in the context of quantum mechanics, relativistic quantum mechanics and quantum field theory, and with applications in the mathematical formulation of the standard model and condensed matter physics. In general, symmetry in physics, invariance, and conservation laws, are fundamentally important constraints for formulating physical theories and models. In practice, they are powerful methods for solving problems and predicting what can happen. While conservation laws do not always give the answer to the problem directly, they form the correct constraints and the first steps to solving a multitude of problems.

Causal fermion systems

The theory of causal fermion systems is an approach to describe fundamental physics. It provides a unification of the weak, the strong and the electromagnetic forces with gravity at the level of classical field theory. Moreover, it gives quantum mechanics as a limiting case and has revealed close connections to quantum field theory. Therefore, it is a candidate for a unified physical theory. Instead of introducing physical objects on a preexisting spacetime manifold, the general concept is to derive spacetime as well as all the objects therein as secondary objects from the structures of an underlying causal fermion system. This concept also makes it possible to generalize notions of differential geometry to the non-smooth setting. In particular, one can describe situations when spacetime no longer has a manifold structure on the microscopic scale. As a result, the theory of causal fermion systems is a proposal for quantum geometry and an approach to quantum gravity.


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