100 Years of Quantum Physics:  Pauli’s Exclusion Principle (1924)

One hundred years ago this month, in December 1924, Wolfgang Pauli submitted a paper to Zeitschrift für Physik that provided the final piece of the puzzle that connected Bohr’s model of the atom to the structure of the periodic table.  In the process, he introduced a new quantum number into physics that governs how matter as extreme as neutron stars, or as perfect as superfluid helium, organizes itself.

He was led to this crucial insight, not by his superior understanding of quantum physics, which he was grappling with as much as Bohr and Born and Sommerfeld were at that time, but through his superior understanding of relativistic physics that convinced him that the magnetism of atoms in magnetic fields could not be explained through the orbital motion of electrons alone.

Encyclopedia Article on Relativity

Bored with the topics he was being taught in high school in Vienna, Pauli was already reading Einstein on relativity and Emil Jordan on functional analysis before he arrived at the university in Munich to begin studying with Arnold Sommerfeld.  Pauli was still merely a student when Felix Klein approached Sommerfeld to write an article on relativity theory for his Encyclopedia of Mathematical Sciences.  Sommerfeld by that time was thoroughly impressed with Pauli’s command of the subject and suggested that he write the article.


Pauli’s encyclopedia article on relativity expanded to 250 pages and was published in Klein’s fifth volume in 1921 when Pauli was only 21 years old—just 5 years after Einstein had published his definitive work himself!  Pauli’s article is still considered today one of the clearest explanations of both special and general relativity.

Pauli’s approach established the methodical use of metric space concepts that is still used today when teaching introductory courses on the topic.  This contrasts with articles written only a few years earlier that seem archaic by comparison—even Einstein’s paper itself.  As I recently read through his article, I was struck by how similar it is to what I teach from my textbook on modern dynamics to my class at Purdue University for junior physics majors.

Fig. 1 Wolfgang Pauli [Image]

Anomalous Zeeman Effect

In 1922, Pauli completed his thesis on the properties of water molecules and began studying a phenomenon known as the anomalous Zeeman effect.  The Zeeman effect is the splitting of optical transitions in atoms under magnetic fields.  The electron orbital motion couples with the magnetic field through a semi-classical interaction between the magnetic moment of the orbital and the applied magnetic field, producing a contribution to the energy of the electron that is observed when it absorbs or emits light. 

The Bohr model of the atom had already concluded that the angular momentum of electron orbitals was quantized into integer units.  Furthermore, the Stern-Gerlach experiment of 1922 had shown that the projection of these angular momentum states onto the direction of the magnetic field was also quantized.  This was known at the time as “space quantization”.  Therefore, in the Zeeman effect, the quantized angular momentum created quantized energy interactions with the magnetic field, producing the splittings in the optical transitions.

File:Breit-rabi-Zeeman-en.svg
Fig. 2 The magnetic Zeeman splitting of Rb-87 from the weak field to the strong-field (Pachen-Back) effect

So far so good.  But then comes the problem with the anomalous Zeeman effect.

In the Bohr model, all angular momenta have integer values.  But in the anomalous Zeeman effect, the splittings could only be explained with half integers.  For instance, if total angular momentum were equal to one-half, then in a magnetic field it would produce a “doublet” with +1/2 and -1/2 space quantization.  An integer like L = 1 would produce a triplet with +1, 0, and -1 space quantization.  Although doublets of the anomalous Zeeman effect were often observed, half-integers were unheard of (so far) in the quantum numbers of early quantum physics.

But half integers were not the only problem with “2”s in the atoms and elements.  There was also the problem of the periodic table. It, too, seemed to be constructed out of “2”s, multiplying a sequence of the difference of squares.

The Difference of Squares

The difference of squares has a long history in physics stretching all the way back to Galileo Galilei who performed experiments around 1605 on the physics of falling bodies.  He noted that the distance traveled in successive time intervals varied as the difference 12 – 02 = 1, then 22-12 = 3, then 32-22 = 5, then 42-32 = 7 and so on.  In other words, the distances traveled in each successive time interval varied as the odd integers.  Galileo, ever the astute student of physics, recognized that the distance traveled by an accelerating body in a time t varied as the square of time t2.  Today, after Newton, we know that this is simply the dependence of distance for an accelerating body on the square of time s = (1/2)gt2

By early 1924 there was another law of the difference of squares.  But this time the physics was buried deep inside the new science of the elements, put on graphic display through the periodic table. 

The periodic table is constructed on the difference of squares.  First there is 2 for hydrogen and helium.  Then another 2 for lithium and beryllium, followed by 6 for B, C, N, O, F and Ne to make a total of 8.  After that there is another 8 plus 10 for the sequence of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn to make a total of 18.  The sequence of 2-8-18 is 2•12 = 2, 2•22 = 8, 2•32 = 18 for the sequence 2n2

Why the periodic table should be constructed out of the number 2 times the square of the principal quantum number n was a complete mystery.  Sommerfeld went so far as to call the number sequence of the periodic table a “cabalistic” rule. 

The Bohr Model for Many Electrons

It is easy to picture how confusing this all was to Bohr and Born and others at the time.  From Bohr’s theory of the hydrogen atom, it was clear that there were different energy levels associated with the principal quantum number n, and that this was related directly to angular momentum through the motion of the electrons in the Bohr orbitals. 

But as the periodic table is built up from H to He and then to Li and Be and B, adding in successive additional electrons, one of the simplest questions was why the electrons did not all reside on the lowest energy level?  But even if that question could not be answered, there was the question of why after He the elements Li and Be behaved differently than B, N, O and F, leading to the noble gas Ne.  From normal Zeeman spectroscopy as well as x-ray transitions, it was clear that the noble gases behaved as the core of succeeding elements, like He for Li and Be and Ne for Na and Mg.

To grapple with all of this, Bohr had devised a “building up” rule for how electrons were “filling” the different energy levels as each new electron of the next element was considered.  The noble-gas core played a key role in this model, and the core was also assumed to be contributing to both the normal Zeeman effect as well as the anomalous Zeeman effect with its mysterious half-integer angular momenta.

But frankly, this core model was a mess, with ad hoc rules on how the additional electrons were filling the energy levels and how they were contributing to the total angular momentum.

This was the state of the problem when Pauli, with his exceptional understanding of special relativity, began to dig deep into the problem.  Since the Zeeman splittings were caused by the orbital motion of the electrons, the strongly bound electrons in high-Z atoms would be moving at speeds near the speed of light.  Pauli therefore calculated what the systematic effects would be on the Zeeman splittings as the Z of the atoms got larger and the relativistic effects got stronger.

He calculated this effect to high precision, and then waited for Landé to make the measurements.  When Landé finally got back to him, it was to say that there was absolutely no relativistic corrections for Thallium (Z = 90).  The splitting remained simply fixed by the Bohr magneton value with no relativistic effects.

Pauli had no choice but to reject the existing core model of angular momentum and to ascribe the Zeeman effects to the outer valence electron.  But this was just the beginning.

Pauli’s Breakthrough

https://onionesquereality.wordpress.com/wp-content/uploads/2012/07/wolfgang-pauli.jpg
Fig. 5 Wolfgang Pauli [Image]

By November of 1924 Pauli had concluded, in a letter to Landé

“In a puzzling, non-mechanical way, the valence electron manages to run about in two states with the same k but with different angular momenta.”

And in December of 1924 he submitted his work on the relativistic effects (or lack thereof) to Zeitschrift für Physik,

“From this viewpoint the doublet structure of the alkali spectra as well as the failure of Larmor’s theorem arise through a specific, classically  non-describable sort of Zweideutigkeit (two-foldness) of the quantum-theoretical properties of the valence electron. (Pauli, 1925a, pg. 385)

Around this time, he read a paper by Edmund Stoner in the Philosophical Magazine of London published in October of 1924.  Stoner’s insight was a connection between the number of states observed in a magnetic field and the number of states filled in the successive positions of elements in the periodic table.  Stoner’s insight led naturally to the 2-8-18 sequence for the table, although he was still thinking in terms of the quantum numbers of the core model of the atoms.

This is when Pauli put 2 plus 2 together: He realized that the states of the atom could be indexed by a set of 4 quantum numbers: n-the principal quantum number, k1-the angular momentum, m1-the space quantization number, and a new fourth quantum number m2 that he introduced but that had, as yet, no mechanistic explanation.  With these four quantum numbers enumerated, he then made the major step:

It should be forbidden that more than one electron, having the same equivalent quantum numbers, can be in the same state.  When an electron takes on a set of values for the four quantum numbers, then that state is occupied.

This is the Exclusion Principle:  No two electrons can have the same set of quantum numbers.  Or equivalently, no electron state can be occupied by two electrons.

Fig. 6 Level filling for Krypton using the Pauli Exclusion Principle

Today, we know that Pauli’s Zweideutigkeit is electron spin, a concept first put forward in 1925 by the American physicist Ralph Kronig and later that year by George Uhlenbeck and Samuel Goudsmit.



And Pauli’s Exclusion Principle is a consequence of the antisymmetry of electron wavefunctions first described by Paul Dirac in 1926 after the introduction of wavefunctions into quantum theory by Erwin Schrödinger earlier that year.

Fig. 7 The periodic table today.

Timeline:

1845 – Faraday effect (rotation of light polarization in a magnetic field)

1896 – Zeeman effect (splitting of optical transition in a magnetic field)

1897 – Anomalous Zeeman effect (half-integer splittings)

1902 – Lorentz and Zeeman awarded Nobel prize (for electron theory)

1921 – Paschen-Back effect (strong-field Zeeman effect)

1922 – Stern-Gerlach (space quantization)

1924 – de Broglie matter waves

1924 – Bose statistics of photons

1924 – Stoner (conservation of number of states)

1924 – Pauli Exclusion Principle

References:

E. C. Stoner (Philosophical Magazine, 48 [1924], 719) Issue 286  October 1924

M. Jammer, The conceptual development of quantum mechanics (Los Angeles, Calif.: Tomash Publishers, Woodbury, N.Y. : American Institute of Physics, 1989).

M. Massimi, Pauli’s exclusion principle: The origin and validation of a scientific principle (Cambridge University Press, 2005).

Pauli, W. Über den Einfluß der Geschwindigkeitsabhängigkeit der Elektronenmasse auf den Zeemaneffekt. Z. Physik 31, 373–385 (1925). https://doi.org/10.1007/BF02980592

Pauli, W. (1925). “Über den Zusammenhang des Abschlusses der Elektronengruppen im Atom mit der Komplexstruktur der Spektren”. Zeitschrift für Physik. 31 (1): 765–783

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The Ubiquitous George Uhlenbeck

There are sometimes individuals who seem always to find themselves at the focal points of their times.  The physicist George Uhlenbeck was one of these individuals, showing up at all the right times in all the right places at the dawn of modern physics in the 1920’s and 1930’s. He studied under Ehrenfest and Bohr and Born, and he was friends with Fermi and Oppenheimer and Oskar Klein.  He taught physics at the universities at Leiden, Michigan, Utrecht, Columbia, MIT and Rockefeller.  He was a wide-ranging theoretical physicist who worked on Brownian motion, early string theory, quantum tunneling, and the master equation.  Yet he is most famous for the very first thing he did as a graduate student—the discovery of the quantum spin of the electron.

Electron Spin

G. E. Uhlenbeck, and S. Goudsmit, “Spinning electrons and the structure of spectra,” Nature 117, 264-265 (1926).

George Uhlenbeck (1900 – 1988) was born in the Dutch East Indies, the son of a family with a long history in the Dutch military [1].  After the father retired to The Hague, George was expected to follow the family tradition into the military, but he stumbled onto a copy of H. Lorentz’ introductory physics textbook and was hooked.  Unfortunately, to attend university in the Netherlands at that time required knowledge of Greek and Latin, which he lacked, so he entered the Institute of Technology in Delft to study chemical engineering.  He found the courses dreary. 

Fortunately, he was only a few months into his first semester when the language requirement was dropped, and he immediately transferred to the University of Leiden to study physics.  He tried to read Boltzmann, but found him opaque, but then read the famous encyclopedia article by the husband and wife team of Paul and Tatiana Ehrenfest on statistical mechanics (see my Physics Today article [2]), which became his lifelong focus.

After graduating, he continued into graduate school, taking classes from Ehrenfest, but lacking funds, he supported himself by teaching classes at a girls high school, until he heard of a job tutoring the son of the Dutch ambassador to Italy.  He was off to Rome for three years, where he met Enrico Fermi and took classes from Tullio Bevi-Cevita and Vito Volterra.

However, he nearly lost his way.  Surrounded by the rich cultural treasures of Rome, he became deeply interested in art and was seriously considering giving up physics and pursuing a degree in art history.  When Ehrenfest got wind of this change in heart, he recalled Uhlenbeck in 1925 to the Netherlands and shrewdly paired him up with another graduate student, Samuel Goudsmit, to work on a new idea proposed by Wolfgang Pauli a few months earlier on the exclusion principle.

Pauli had explained the filling of the energy levels of atoms by introducing a new quantum number that had two values.  Once an energy level was filled by two electrons, each carrying one of the two quantum numbers, this energy level “excluded” any further filling by other electrons. 

To Uhlenbeck, these two quantum numbers seemed as if they must arise from some internal degree of freedom, and in a flash of insight he imagined that it might be caused if the electron were spinning.  Since spin was a form of angular momentum, the spin degree of freedom would combine with orbital angular momentum to produce a composite angular momentum for the quantum levels of atoms.

The idea of electron spin was not immediately embraced by the broader community, and Bohr and Heisenberg and Pauli had their reservations.  Fortunately, they all were traveling together to attend the 50th anniversary of Lorentz’ doctoral examination and were met at the train station in Leiden by Ehrenfest and Einstein.  As usual, Einstein had grasped the essence of the new physics and explained how the moving electron feels an induced magnetic field which would act on the magnetic moment of the electron to produce spin-orbit coupling.  With that, Bohr was convinced.

Uhlenbeck and Goudsmit wrote up their theory in a short article in Nature, followed by a short note by Bohr.  A few months later, L. H. Thomas, while visiting Bohr in Copenhagen, explained the factor of two that appears in (what later came to be called) Thomas precession of the electron, cementing the theory of electron spin in the new quantum mechanics.

5-Dimensional Quantum Mechanics

P. Ehrenfest, and G. E. Uhlenbeck, “Graphical illustration of De Broglie’s phase waves in the five-dimensional world of O Klein,” Zeitschrift Fur Physik 39, 495-498 (1926).

Around this time, the Swedish physicist Oskar Klein visited Leiden after returning from three years at the University of Michigan where he had taken advantage of the isolation to develop a quantum theory of 5-dimensional spacetime.  This was one of the first steps towards a grand unification of the forces of nature since there was initial hope that gravity and electromagnetism might both be expressed in terms of the five-dimensional space.

An unusual feature of Klein’s 5-dimensional relativity theory was the compactness of the fifth dimension, in which it was “rolled up” into a kind of high-dimensional string with a tiny radius.  If the 4-dimensional theory of spacetime was sometimes hard to visualize, here was an even tougher problem.

Uhlenbeck and Ehrenfest met often with Klein during his stay in Leiden, discussing the geometry and consequences of the 5-dimensional theory.  Ehrenfest was always trying to get at the essence of physical phenomena in the simplest terms.  His famous refrain was “Was ist der Witz?” (What is the point?) [1].  These discussions led to a simple paper in Zeitschrift für Physik published later that year in 1926 by Ehrenfest and Uhlenbeck with the compelling title “Graphical Illustration of De Broglie’s Phase Waves in the Five-Dimensional World of O Klein”.  The paper provided the first visualization of the 5-dimensional spacetime with the compact dimension.  The string-like character of the spacetime was one of the first forays into modern day “string theory” whose dimensions have now expanded to 11 from 5.

During his visit, Klein also told Uhlenbeck about the relativistic Schrödinger equation that he was working on, which would later become the Klein-Gordon equation.  This was a near miss, because what the Klein-Gordon equation was missing was electron spin—which Uhlenbeck himself had introduced into quantum theory—but it would take a few more years before Dirac showed how to incorporate spin into the theory.

Brownian Motion

G. E. Uhlenbeck and L. S. Ornstein, “On the theory of the Brownian motion,” Physical Review 36, 0823-0841 (1930).

After spending time with Bohr in Copenhagen while finishing his PhD, Uhlenbeck visited Max Born at Göttingen where he met J. Robert Oppenheimer who was also visiting Born at that time.  When Uhlenbeck traveled to the United States in late summer of 1927 to take a position at the University of Michigan, he was met at the dock in New York by Oppenheimer.

Uhlenbeck was a professor of physics at Michigan for eight years from 1927 to 1935, and he instituted a series of Summer Schools [3] in theoretical physics that attracted international participants and introduced a new generation of American physicists to the rigors of theory that they previously had to go to Europe to find. 

In this way, Uhlenbeck was part of a great shift that occurred in the teaching of graduate-level physics of the 1930’s that brought European expertise to the United States.  Just a decade earlier, Oppenheimer had to go to Göttingen to find the kind of education that he needed for graduate studies in physics.  Oppenheimer brought the new methods back with him to Berkeley, where he established a strong theory department to match the strong experimental activities of E. O. Lawrence.  Now, European physicists too were coming to America, an exodus accelerated by the increasing anti-Semitism in Europe under the rise of fascism. 

During this time, one of Uhlenbeck’s collaborators was L. S. Ornstein, the director of the Physical Laboratory at the University of Utrecht and a founding member of the Dutch Physical Society.  Uhlenbeck and Ornstein were both interested in the physics of Brownian motion, but wished to establish the phenomenon on a more sound physical basis.  Einstein’s famous paper of 1905 on Brownian motion had made several Einstein-style simplifications that stripped the complicated theory to its bare essentials, but had lost some of the details in the process, such as the role of inertia at the microscale.

Uhlenbeck and Ornstein published a paper in 1930 that developed the stochastic theory of Brownian motion, including the effects of particle inertia. The stochastic differential equation (SDE) for velocity is

where γ is viscosity, Γ is a fluctuation coefficient, and dw is a “Wiener process”. The Wiener differential dw has unusual properties such that

Uhlenbeck and Ornstein solived this SDE to yield an average velocity

which decays to zero at long times, and a variance

that asymptotes to a finite value at long times. The fluctuation coefficient is thus given by

for a process with characteristic speed v0. An estimate for the fluctuation coefficient can be obtained by considering the force F on an object of size a

For instance, for intracellular transport [4], the fluctuation coefficient has a rough value of Γ = 2 Hz μm2/sec2.

Quantum Tunneling

D. M. Dennison and G. E. Uhlenbeck, “The two-minima problem and the ammonia molecule,” Physical Review 41, 313-321 (1932).

By the early 1930’s, quantum tunnelling of the electron through classically forbidden regions of potential energy was well established, but electrons did not have a monopoly on quantum effects.  Entire atoms—electrons plus nucleus—also have quantum wave functions and can experience regions of classically forbidden potential.

Uhlenbeck, with David Dennison, a fellow physicist at Ann Arbor, Michigan, developed the first quantum theory of molecular tunneling for the molecular configuration of ammonia NH3 that can tunnel between the two equivalent configurations. Their use of the WKB approximation in the paper set the standard for subsequent WKB approaches that would play an important role in the calculation of nuclear decay rates.

Master Equation

A. Nordsieck, W. E. Lamb, and G. E. Uhlenbeck, “On the theory of cosmic-ray showers I. The furry model and the fluctuation problem,” Physica 7, 344-360 (1940)

In 1935, Uhlenbeck left Michigan to take up the physics chair recently vacated by Kramers at Utrecht.  However, watching the rising Nazism in Europe, he decided to return to the United States, beginning as a visiting professor at Columbia University in New York in 1940.  During his visit, he worked with W. E. Lamb and A. Nordsieck on the problem of cosmic ray showers. 

Their publication on the topic included a rate equation that is encountered in a wide range of physical phenomena. They called it the “Master Equation” for ease of reference in later parts of the paper, but this phrase stuck, and the “Master Equation” is now a standard tool used by physicists when considering the balances among multiples transitions.

Uhlenbeck never returned to Europe, moving among Michigan, MIT, Princeton and finally settling at Rockefeller University in New York from where he retired in 1971.

By David D. Nolte, April 24, 2024

Selected Works by George Uhlenbeck:

G. E. Uhlenbeck, and S. Goudsmit, “Spinning electrons and the structure of spectra,” Nature 117, 264-265 (1926).

P. Ehrenfest, and G. E. Uhlenbeck, “On the connection of different methods of solution of the wave equation in multi dimensional spaces,” Proceedings of the Koninklijke Akademie Van Wetenschappen Te Amsterdam 29, 1280-1285 (1926).

P. Ehrenfest, and G. E. Uhlenbeck, “Graphical illustration of De Broglie’s phase waves in the five-dimensional world of O Klein,” Zeitschrift Fur Physik 39, 495-498 (1926).

G. E. Uhlenbeck, and L. S. Ornstein, “On the theory of the Brownian motion,” Physical Review 36, 0823-0841 (1930).

D. M. Dennison, and G. E. Uhlenbeck, “The two-minima problem and the ammonia molecule,” Physical Review 41, 313-321 (1932).

E. Fermi, and G. E. Uhlenbeck, “On the recombination of electrons and positrons,” Physical Review 44, 0510-0511 (1933).

A. Nordsieck, W. E. Lamb, and G. E. Uhlenbeck, “On the theory of cosmic-ray showers I The furry model and the fluctuation problem,” Physica 7, 344-360 (1940).

M. C. Wang, and G. E. Uhlenbeck, “On the Theory of the Brownian Motion-II,” Reviews of Modern Physics 17, 323-342 (1945).

G. E. Uhlenbeck, “50 Years of Spin – Personal Reminiscences,” Physics Today 29, 43-48 (1976).

Notes:

[1] George Eugene Uhlenbeck: A Biographical Memoire by George Ford (National Academy of Sciences, 2009). https://www.nasonline.org/publications/biographical-memoirs/memoir-pdfs/uhlenbeck-george.pdf

[2] D. D. Nolte, “The tangled tale of phase space,” Physics Today 63, 33-38 (2010).

[3] One of these was the famous 1948 Summer School session where Freeman Dyson met Julian Schwinger after spending days on a cross-country road trip with Richard Feynman. Schwinger and Feynman had developed two different approaches to quantum electrodynamics (QED), which Dyson subsequently reconciled when he took up his position later that year at Princeton’s Institute for Advanced Study, helping to launch the wave of QED that spread out over the theoretical physics community.

[4] D. D. Nolte, “Coherent light scattering from cellular dynamics in living tissues,” Reports on Progress in Physics 87 (2024).


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