Despite the success of Schrödinger’s description of the H-atom, it became apparent that the spectrum of the simplest multi-electron atom—helium—could not be so readily explained. And the spectra of other atoms showed ‘anomalous’ splitting in a magnetic field. In 1920 Sommerfeld introduced a fourth quantum number. A few years later Pauli was led to the inspired conclusion that the electron must have a curious ‘two-valuedness’ characterized by a quantum number of ½, and went on to discover the exclusion principle. Perhaps this is because the electron possesses a self-rotation, leading to the notion of electron spin, potentially explaining why each orbital can accommodate only two electrons. Heisenberg traced this behaviour back to the symmetry properties of the wavefunctions. By observing which transitions in the spectrum of helium are allowed and which are forbidden, we can deduce the generalized Pauli principle, from which the exclusion principle follows.
Despite the success of Schrödinger’s description of the H-atom, it became apparent that the spectrum of the simplest multi-electron atom—helium—could not be so readily explained. And the spectra of other atoms showed ‘anomalous’ splitting in a magnetic field. In 1920 Sommerfeld introduced a fourth quantum number. A few years later Pauli was led to the inspired conclusion that the electron must have a curious ‘two-valuedness’ characterized by a quantum number of ½, and went on to discover the exclusion principle. Perhaps this is because the electron possesses a self-rotation, leading to the notion of electron spin, potentially explaining why each orbital can accommodate only two electrons. Heisenberg traced this behaviour back to the symmetry properties of the wavefunctions. By observing which transitions in the spectrum of helium are allowed and which are forbidden, we can deduce the generalized Pauli principle, from which the exclusion principle follows.
The exclusion principle was the final outcome of Pauli's struggle to understand some spectroscopic anomalies in the early 1920s: doublets were observed in the spectra of alkali metals, singlets and triplets in the spectra of the alkaline earths, and even more anomalous patterns were observed when chemical elements were placed in an external magnetic field (anomalous Zeeman effect and Paschen–Back effect). These anomalous spectra challenged the old quantum theory, and prompted a radical theoretical change (Section 2.1). From 1920 to 1924 Alfred Landé, Werner Heisenberg, and Niels Bohr were all engaged in trying to save the traditional spectroscopic model (the so-called atomic core model) and to reconcile it with the observed anomalies. The impasse was solved only with Pauli's introduction of a fourth degree of freedom for the electron, and the consequent demise of the atomic core model (Section 2.2). What Pauli called the ‘twofoldness’ [ Zweideutigkeit ] of the electron's angular momentum was soon reinterpreted as the electron's spin (Section 2.3). Pauli's exclusion rule was announced in this semi-classical spectroscopic context that characterized the revolutionary transition from the old quantum theory to the new quantum theory around 1925. The prehistory of Pauli's exclusion principle Atomic spectra and the Bohr–Sommerfeld theory of atomic structure The existence of spectral lines had been known to scientists since the beginning of the nineteenth century when Wollaston and Fraunhofer first observed the dark absorption lines in the spectrum of the Sun.
The history of the exclusion principle is already an old one, but its conclusion has not yet been written. It is now eighty years since Wolfgang Pauli introduced an ‘extremely natural’ prescriptive rule, while dealing with some spectroscopic anomalies that beset physicists in the heyday of the old quantum theory. The rule excluded the possibility that any two bound electrons in an atom were in the same dynamic state, identified by a set of four quantum numbers. Hence the name of Ausschlieβungsregel (exclusion rule), or Pauli's Verbot (Pauli's veto) as Werner Heisenberg nicknamed it. The far-reaching physical significance of this rule became clear only later. From spectroscopy to atomic physics, from quantum field theory to high-energy physics, there is hardly another scientific principle that has more far-reaching implications than Pauli's exclusion principle. It is thanks to Pauli's principle that one obtains the electronic configurations underlying the classification of chemical elements in Mendeleev's periodic table as well as atomic spectra. To this same principle we credit the statistical behaviour of any half-integral spin particles (protons, neutrons, among many others) and the stability of matter. Shifting to high-energy physics, it is the exclusion principle that fixes the crucial constraint for binding quarks in hadrons, which together with leptons compose our physical world. This book advances a philosophical analysis of the enduring and far-reaching validity of Pauli's principle. It does not aim to address what a scientific principle is.
Shortly after their introduction, the electron's Zweideutigkeit and Pauli's Ausschliessungsregel were embedded into a growing theoretical framework: from Fermi–Dirac statistics in 1926 (Section 4.2), to the non-relativistic quantum mechanics of the magnetic electron with Pauli's spin matrices in 1927 (Section 4.3); from Wigner and von Neumann's group theoretical derivation of the spin matrices in 1927 (Section 4.4), to Jordan's reinterpretation of Pauli's exclusion principle in terms of anticommutation relations for particle creation and annihilation operators in 1928 (Section 4.5), which paved the way for quantum field theory. The most important step in building up this theoretical framework was the transition from non-relativistic to relativistic quantum mechanics, with Dirac's equation for the electron in 1928 (Section 4.6), which finally allowed the derivation of the electron's spin with its anomalous magnetic moment and hence clarified in a conclusive way the origin of spectroscopic anomalies. The negative energy solutions of the Dirac equation, and Dirac's attempt to accommodate them via the hole theory in 1930, anticipated the experimental discovery of the antiparticle of the electron, the positron. Sections 4.7-4.9 reconstruct Pauli's sustained criticism of Dirac's hole theory. The history of this debate is intertwined with Pauli's search for a spin–statistics connection, which finally culminated in the spin–statistics theorem in 1940. With this theorem, the nomological shift from the status of a phenomenological rule to that of a fundamental scientific principle is finally completed. Introduction The year 1925 was the annus mirabilis for quantum mechanics.
Abstract Section I.—The exclusion principle of Pauli was introduced into the old quantum theory as an empirical fact that had been brought to light in the ordering of spectra. The new mechanics has provided some sort of explanation of the principle, for in a closed system with many electrons the mathematically possible stationary states can be separated into a number of groups, with the property that transitions between stationary states in different groups cannot occur. One of these group is made up of the stationary states corresponding occur. One of the these groups is made up of the stationary states corresponding to wave functions that are antisymmetrical in the co-ordinates of the electrons. Apart from accidental degeneracies, the stationary states in different groups have different energy values. The exclusion principle then states that only energy values belonging to the antisymmertical group are found in nature. The exclusion principle has had great success not only in explaining the spectra of helium and of more complicated atoms, but also, under the form of the Fermi-Dirac statistics, in accounting for metallic conduction and ferromagnetism. In all these phenomena we are dealing with systems is stationary states, possessing energy values which are discrete, although they may lie very close together. Now, as was first emphasised by Oppenheimer, we must also use antisymmetrical wave-functions to describe aperiodic phenomena, such as the collision between an electron and an atom. If we do not, we obtain probabilities for the formation of atoms whose wave-funtions are not antisymmetrical, as we shall show in section 4, where we consider the collision between an electron and a helium atom. A helium atom described by a symmetrical wave-function would show a singlet series in palce of the observed triplets and triplet series in place of the observed singlets. The wave-functions of open systems are essentially degenerate; the symmetical and antisymmetrical solution are not separated from one another by a finite energy difference; but for any arbitrary value of the energy (and of the other integrals of the motion) we can form a symmetrical and an antisymmetrical solution. This is somewhat fundamental difference between open and closed systems. For closed systems containing two electrons there exist only the symmetrical and the antisymmetical solution; but for open systems we might take any combination of the two. In fact, to describe an observable phenomenon such as a collision, the wave-function that it would first occur to us to use is a combination of the two. To fix our ideas we shall discuss the collision between two electrons. Our arguments could equally well be applied to the collision between an electron and a hydrogen atom, the problem originally discussed by Born; but the former is the simpler case, and perhaps illustrates our theory better.
Abstract De Broglie’s wavelength for a particle is used to explain the Heisenberg Uncertainty principle. Determinism is replaced by wave mechanics based on the probability of decay through exit channels. The concepts of spin and parity are explained with contributions from Pauli, Ralph de Laer Kronig, Samual Goudsmit, and George Uhlenbeck. Sommerfeld uses quantum numbers to explain atomic spectra. Pauli uses observations of the anomalous Zeeman effect to suggest new quantum numbers based on the electron having an additional two-value property, spin. Lee and Yang show parity is not always conserved. The theory of alpha decay using George Gamow’s tunnelling explanation and Fermi’s explanation of beta decay following Pauli’s suggestion of spin and the prediction of the neutrino complete the explanation of radioactivity. Dirac predicts antimatter and positron decay is observed. James Chadwick discovers the neutron.
Atomic spectra had twice as many lines as predicted. As a solution, two young physicists, George Uhlenbeck and Samuel Goudsmit, proposed that in addition to orbiting its nucleus, an electron “spins” around its axis. (Not really, but the idea works.) Wolfgang Pauli showed that the spin could only have two opposing orientations. This could account for all of the lines. He further proposed an “Exclusion Principle”: that no electrons could be described by all the same quantum numbers, otherwise atoms (and we) could not exist. In 1930, he predicted the existence of a new particle, the neutrino, which was not observed until 26 years later. In addition to contributions to quantum mechanics, Pauli was famous for nasty remarks. A couple of gems:“This paper is so bad it is not even wrong.”“I don't mind your thinking slowly; I mind your publishing faster than you think.”