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 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.
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 aim of this book was to investigate the rationale for Pauli's principle, and the conditions under which we are justified in regarding a phenomenological and contingent rule as an important scientific principle. To this purpose, I urged a Kantian perspective. As a conclusion, I want to foreshadow how this perspective relates to contemporary discussions about images of science, and how it bears upon the on-going debate on scientific realism in philosophy of science. I shall barely scratch the surface of this complex topic and its vast literature. The best I can do in these concluding remarks is to suggest a philosophical position that I think deserves to be further explored. What follows should then be read more as an outline for future research, than as a conclusion. I began this book by reconstructing the origins of the exclusion principle as a phenomenological rule arising from the spectroscopic research of the 1920s. I argued that the rule was derived – in conjunction with the concept of the electron's Zweideutigkeit – from spectroscopic phenomena with the help of some theoretical assumptions, in the period of revolutionary transition from the old to the new quantum theory. I defended the prospective intelligibility of this revolutionary transition in the light of the piecemeal process of transformation of the old quantum theory, from which brand new scientific concepts and nomic generalizations followed.
The origin of the new quantum mechanics was an epoch-making memoir by Werner Heisenberg which contained the new concept which was to lead to the phenomenal developments of quantum mechanics of the past two years. Up to this time the quantum theory (the ‘older’ quantum theory) postulated the existence of stationary states of the atom calculated by the use of the classical mechanics and selected by the use of quantum conditions satisfied by the action variables of that theory. In the new mechanics the equations have the same form as in the classical theory, but the variables no longer satisfy the commutative law of multiplication, that is, xy is not in general equal to yx ; the quantum conditions of the older theory are replaced by equations which enable the difference xy – yx to be calculated; these equations involve Planck's constant h. For some years before 1925, Sommerfeld, Heisenberg, Landé and Pauli had been grappling with the complex problem of the multiplets and their Zeeman separations. By the use of a system of quantum numbers l, s, j connected with the respective angular momenta of the series electron, the core, and the whole atom, they had given a qualitative account of the multiplets of the alkalis, alkaline earths, etc., the work culminating in a very general empirical formula—the g -formula of Landé—which enabled the Zeeman separations of a multiplet to be worked out quantitatively in terms of the quantum numbers l, s, j.
Abstract The development of the complex of assumptions and methods now referred to as the “old quantum theory” mainly took place in the first five years following the introduction of the Bohr atomic model in 1913. Three guiding principles emerged that were used, sometimes in overlapping ways, to explain the flood of spectroscopic data that needed to be explained. First, quantization rules (or conditions) were proposed to single out the allowed orbital motions of electrons in atoms. These rules were derived in various forms by Planck, Sommerfeld, and Wilson, but were put into their most general form by Schwarzschild, who recognized the underlying principle as the quantization of the action variables of a multiply periodic classical system. Second, the special role of the action variables in quantization was given convincing support by the transfer of the adiabatic principle of mechanics to quantum theory (work primarily due to Paul Ehrenfest). Third, the correspondence principle, or statement of asymptotic coincidence of quantum and classical theory in the limit of large quantum numbers, originally introduced by Bohr in 1913 as a supporting argument for his quantization of angular momentum in his theory of the hydrogen atom, was extended by Bohr and Kramers to provide selection rules and approximate intensity predictions evening the regime low quantum numbers.