Mark J.

Moody Honors Quantum Mechanics 4-26-2013

The History of Electron Spin

Contrary to common sense and semantics, electrons do not physically spin. Electron spin is an intrinsic form of angular momentum carried by an electron, the name spin carrying over from a classical analog reminiscent of a planet not only orbiting about a celestial body, but also spinning on its axis. Over time, this conception proved incorrect, but the name remains. In reality, no part of an electron is physically spinning and we have no entirely accurate classical analog to describe the property of spin. Unlike physically spinning objects, electron spin can take on half integer values, the direction of spin can be changed but its speed cannot, and the magnetic induction necessary to explain the observed magnetic dipole moment of an electron requires a different internal charge distribution than the measured, accepted value. Electron spin is a purely quantum mechanical effect. Electrons have been shown through Youngs double slit diffraction experiment and observed discreet atomic energy levels to exhibit wave like behavior, and are best described as a wave function generally represented by with an additional term

outside the wave function representative of spin since spin does not alter the wave function itself. Everything we know about a particle can be derived from the particles wave function and spin. Four quantized values known as quantum numbers characterize the complete and unique quantum wave function of any electron: n, l, m, and s. The principal quantum number, n, is a positive integer which determines the size of the electron orbital and the energy of the electron(s) associated with that shell. Each electron shell can hold electrons. As n increases, orbital

size increases, allowing an electron to exist at a greater radial distance from the positively charged nucleus. This separation of charge increases the potential energy between the electron and nucleus and so determines the electrons energy for that state. For single electron systems such as is found in a hydrogen atom, an electrons energy depends exclusively upon n. For multi electron systems, the electrons energy also depends upon l.

The azimuthal quantum number, l, is an integer ranging from zero to

which defines

angular momentum and the three dimensional shape of the orbital. Similar to the above described method for organizing orbitals into shells according to n, orbitals within a shell are also grouped into subshells according to l. The letters s, p, d, and f are typically used to describe the value for l, zero being s, one being p, two being d, three being f, and any integer four or greater following alphabetically using g,h,i and so on. The letters s, p, d, and f originally came from descriptions of atomic spectra, and indicate sharp, principal, diffuse, and fundamental, respectively. An orbital with principal quantum number 2 and azimuthal quantum number 1 would be a orbital.

The magnetic quantum number, m, is an integer ranging from l to l describing the spatial orientation of the electron orbital, loosely indicating the direction of the angular momentum vector. While m does not influence the electrons energy, it affects the space quantization of the electrons probability cloud. The 2l+1 values for m restrict the portion of the total angular momentum along a particular quantization axis in agreement with Heisenbergs uncertainty principle. For each subshell l, there are 2l+1 unique spatial orientations for the comprising orbitals. As the simplest example, the z component of an electrons angular momentum, with respect to a standard Cartesian coordinate system, upon reduction, is given by . [2]

The azimuthal quantum number yields the quantum mechanical analog to classical angular momentum For both cases case, where classically and quantum mechanically. is momentum. In the first

is the radial distance from the center of orbit and

represents the mass of the orbiting object and , where

represents its velocity. In the quantum is Plancks action quantum, and

mechanical case,

is an operator (shown in Cartesian coordinates) that acts upon the wave function . This electron orbital angular momentum is very similar to the classical notion of orbital angular momentum. While orbital angular momentum is derived from an electrons rotating trajectory about a nucleus, spin angular momentum is inferred from experiments such as the Stern-Gerlach experiment, in which orbital angular momentum cannot account for all of the observed angular momentum effects. In 1922, Otto Stern and Walther Gerlach performed their now famous experiment on the deflection of particles. The Stern-Gerlach experiment shows that electrons and atoms have intrinsic quantum properties, and exhibits that measurements made on a quantum mechanical system affect the system being measured. This means that a wave function initially existing as a superposition of several eigenstates collapses to a single determinate eigenstate upon interaction or measurement (indeed, measurement of any sort requires interaction). It is this quantum property that relates the wave function of a physically realizable object with the classical observables position and momentum. The Stern-Gerlach experiment involves sending a beam of particles through an inhomogeneous magnetic field and observing their deflection. In such a field, there is a force (in addition to the standard torque) exerted on a magnetic dipole, the force being given by , where represents the magnetic dipole and represents the magnetic vector field.

Were the dipole produced by physical spin, one would expect the distribution of their spin angular momentum vectors to be continuous. Interestingly, Stern and Gerlach observed discreet, consistent values of deflection, either up or down. This means that such particles have quantized magnetic moments of two possible values.

This same experiment was performed for electrons, but since electrons are charged particles, their motion through a magnetic field deflects their trajectory into a curved path proportional to the electrons velocity with an exerted Lorentz force represents charge and where

represents velocity. An appropriate electric field is used to cancel this

force so that measurements can be made regarding the previously defined force in a consistent manner. Electrons were measured to have two possible spin values, , meaning that they are

spin particles, though this interpretation was not discovered until later. [1]

In mid-September of 1925, George Uhlenbeck and Samuel Goudsmit discovered what has become known as electron spin. Goudsmit believed that a great deal of auspicious chance accompanied himself and Uhlenbeck in their discovery. While Goudsmit was a doctoral student at Leiden University, he once needed to accompany his father on a business trip to Germany. Goudsmits professor, Paul Ehrenfest preferred that Goudsmit not interrupt his studies and upon learning Goudsmits destination explained: Nearby is a university and there is a spectroscopist, Paschen. You are interested in spectroscopy; go and have a look. Paschen treated Goudsmit more as a colleague than a student and showed Goudsmit the experimental setup he used for the spectral line of ionized helium. At the time, Goudsmit didnt understand the experiment in its entirety, but noted a few interesting attributes of the helium spectral lines: fine structure, the Sommerfield relativistic explanation, and a forbidden component that was clearly observable. Many theoreticians simply excluded the forbidden component claiming it was due to inaccuracy in experimentation. Soon, Goudsmits interest in spectroscopy let him to discover a formula for the doublets in the helium spectra, and he made the claim that his formula was identical to the formula used

by Sommerfeld for X-ray doublets. Doublets arise from the observation that certain spectral lines of an excited, ionized gas, split into separate lines in the presence of a strong magnetic field. This is also more generally known as the Zeeman effect. Upon telling Ehrenfest about his formula, Ehrenfest saw that it lacked supporting evidence and derivation, but not wanting to discourage Goudsmit, offered to have it published. Goudsmits main article on the topic was published in Holland and in French, resulting in very few people reading the article. Nevertheless, as a young graduate student, Goudsmit was quite proud of the publication. Two and a half years later, Robert Millikan developed the same formula, supported by experimental data confirming its accuracy. Soon thereafter, Ralph Kronig traveled from America to Leiden University and collaborated with Goudsmit in his spectroscopy work including the intensities of the Zeeman effect. Quantum theory was in formulation, and quantum mechanics as a complete subject of study did not yet exist. Goudsmit and Kronig made educated guesses and tested various formulae, developing a feel for each tests correctness. When Ehrenfest learned about Goudsmits inexact testing methods, he sent Goudsmit to Amsterdam to serve as a part-time assistant to Pieter Zeeman, who took a more formal approach in his spectroscopy testing. During this time, Goudsmit recognized that the recent publication of the Pauli principle, despite being one of the most important publications to date in physics, was cumbersome and difficult to understand. Goudsmit felt the principle was more difficult to understand than necessary, and wrote that Paulis principle becomes easier to digest if two new quantized numbers are introduced to the system: and , with always being (Goudsmit

originally used 1 and 0, but the effect is the same and

is the currently accepted value).

Using these quantized numbers with the Pauli principle significantly simplifies it. Goudsmits change didnt fundamentally alter the Pauli principle and is equivalent to a simplistic linear transformation. Though the fundamentals of the Pauli principle werent altered, this new form rendered understanding and teaching much more manageable. By the spring of 1925, the introduction of and as quantum numbers supported that electrons possess quantized spins,

but this feature went unnoticed. Goudsmit wrote a letter to Kronig explaining his discovery of the simplified Pauli principle, but Kronig seemed uninterested, writing back to Goudsmit about several other matters, never mentioning Goudsmits discovery. During this time, George Uhlenbeck interrupted his research to take a position as tutor for the children of the Netherlands Ambassador in Rome. Ehrenfest introduced Uhlenbeck to Goudsmit, telling Goudsmit that Uhlenbeck had learned classical physics in Italy, and recommending the two should work together for Uhlenbeck to learn about atomic structure and spectral analysis. Goudsmit suspected that Ehrenfest really intended the reversethat Ehrenfest wanted Goudsmit to learn some formal classical physics from Uhlenbeck. While Uhlenbeck initially understood little regarding this new physics of atomic spectra, he helped Goudsmit with an article he had promised to write for Physica. Since Uhlenbeck was unfamiliar with the subject, he asked many questions that Goudsmit hadnt previously considered, leading to some significant results. The first result was a new interpretation of the hydrogen spectrum, replacing and updating the Sommerfeld hydrogen spectrum. Since Goudsmit had so familiarized himself with atomic spectra intensity rules and such, he was able to essentially guess which formulae they had to use. Goudsmit and Uhlenbeck used the classical expressions, with the exception of using half

integral quantum numbers rather than integral quantum numbers. This method precisely fit the hydrogen spectrum, even predicting Paschens forbidden spectral line as though it would be present, and indeed, it was. The forbidden spectral line was not in fact forbidden or brought about by erroneous measurements, but a valid spectral line that Goudsmit and Uhlenbecks formulae predicted. Goudsmit and Uhlenbeck had little idea how important their result would become, but nevertheless published their results in Dutch in the Physica journal. They also published a paper in Zeitschrift fur Physik on the quantum vectors and . and

Some time later, Goudsmit introduced Uhlenbeck to the Pauli principle using his

quantum numbers. Uhlenbeck recognized that this quantization implied a fourth degree of freedom for the electron, meaning that it would be expected to spin or rotate. Uhlenbeck did not know of Land or Heisenbergs work, since he was trained classically, and Goudsmit did not know what a degree of freedom was. A degree of freedom is any of the minimum number of coordinates needed to completely specify the motion of a mechanical system. For example, Cartesian coordinates in three dimensions x, y, and z (mutually perpendicular) yield three translational degrees of freedom: up/down, left/right, and forward/backward; and three rotational degrees of freedom: tilting forward/backward, swiveling left/right, and pivoting side to side. When Uhlenbeck made this remark, Goudsmit realized this conception fit precisely with the interpretation of the hydrogen spectrum they had published just four weeks prior. Electromagnetic induction indicates that electric charges and magnetic fields are intrinsically related. A moving charge will induce a magnetic field radially about the charges linear path and a constantly changing magnetic flux will induce an electromotive force on nearby charged particles, resulting in a current when the collection of charged particles move through a conducting wire. If we treat a system of uniformly distributed charges about a sphere, the

spheres rotation would induce a magnetic moment along the axis of rotation. This is the first conception of electron spin. The electron was believed to be physically spinning, inducing a magnetic moment. The magnetic moment is necessary, it fully describes and fits the Zeemaneffect and it came out naturally along with the Land formulae. Goudsmit and Uhlenbeck eagerly informed Ehrenfest, and various other physicists how their model fitted perfectly with the formalism. Goudsmit had an excellent feel for the formulae of atomic spectra but did not understand all of the rigorous physics in the formal model. Uhlenbeck, on the other hand, began to ponder about rotating charges. Uhlenbeck went to Hendrik Lorentz regarding the matter and received the reply, Yes, that is very difficult because it causes the self energy of the electron to be wrong. Goudsmit and Uhlenbeck had just submitted an article to Ehrenfest, who in turn planned to send it off for publication in Naturwissenschaften. Uhlenbeck then urgently traveled to Ehrenfest following his discussion with Lorentz, and requested Ehrenfest not to send the paper to be published. Uhlenbeck had come to realize the impossibility of having an electron that rotates at the necessary high angular velocity (near the speed of light) to induce the observed magnetic moment. Unfortunately, Ehrenfest had already submitted the paper for publication including the now-known erroneous material, and the paper was published under Goudsmit and Uhlenbecks names. When Goudsmit learned of this, Uhlenbecks consoled Goodsmit, Well, that is a nice idea, though it may be wrong. But you dont yet have a reputation, so you have nothing to lose. Following publication of the paper, Heisenberg wrote a letter to Goudsmit and Uhlenbeck referring to their courageous publication. Goudsmit did not find the submission courageous at all, possibly because he had not yet made a public name for himself, or didnt understand the

consequences of submitting erroneous information. In any case, Heisenbergs response incorporated a formula (most of which Goudsmit did not understand, considering the formula was given without derivation) and a question about what Goudsmit and Uhlenbeck had done with the factor two. Goudsmit had not the slightest idea of what factor Heisenberg was referring to or what this implied. Goudsmit and Uhlenbeck discovered electron spin because it fit very nicely into their formalism, but they had never constructed a quantitative calculation regarding the size of the spectral line splitting. If one were to accept the notion of electron spin up or spin down, they were not sure if the discrepancy in energy would be yielded correctly. They had developed convenient formulae fitting with previous knowledge, but had no idea if it were even possible to derive said formulae. Goudsmit believed the derivation process would be incredibly laborious and difficult, but we now know that nearly any physics or chemistry student studies the spectral line of hydrogen at some point and can perform the derivation quite easily. In an odd sense, it seems fortuitous that they had not worked out the derivation, because the discrepancy of the factor of two would have led them to believe their formulae to be incorrect and they may never have published their paper. They believed all the formulae fit together perfectly, but this term seemed to ruin that notion and would have prevented their publication. Understandably, this series of events around publishing an error discouraged both Goudsmit and Uhlenbeck. Fortunately, Lorentz was approaching the fiftieth anniversary of his doctorate degree, and many prominent physicists joined him for a celebration in Leiden, very close to where Goudsmit and Uhlenbeck worked. They all met at Ehrenfests home and

discussed a myriad of topics, including the problem of electron spin. Goudsmit recounts that he learned a great deal during these meetings. Neils Bohr took particular interest in Goudsmit and Uhlenbecks formulae and he reasoned that the factor two could be trivial. Bohr invited Goudsmit to Copenhagen for research opportunities. Goudsmit considered this a mistake, that Bohr should have invited Uhlenbeck instead. Goudsmit did not seem to be making progress over six weeks time, so Bohr sent him back to Hague. While in Copenhagen, Goudsmit met a young man named Thomas who had become proficient in working with Einsteins theory of relativity. Thomas took Goudsmits forlmulae and worked out the factor of two that Heisenberg noticed. Thomas informed Goudsmit that the factor of two represented the relativistic factor and that the formulae were actually correct, just misunderstood. Goudsmit told Bohr about the discovery, and Bohr recommended that he stop in Hamburg on his way home to explain the justification to Pauli. Goudsmit made the attempt, but since his understanding of the derivation and relativistic theory was inadequate, he failed to explain it to Pauli. According to Goudsmit, Pauli seemed to have a predisposition for disbelieving the theory of spin even before the justification, and Goudsmits attempt apparently did nothing to alleviate this. Upon Goudsmits return to Leiden, Einstein was still there, and he again made the attempt to explain his justification. According to Goudsmit, this went even worse, presumably because Einstein developed the theory of relativity and knew the subject intimately. Einstein would therefore be able to quickly point out when Goudsmit was misusing it or misunderstanding it in his supposed justification. Goudsmit left the subject and its justification alone for the time being, but later received a letter from Pauli explaining that Thomas had shown him the work and that he was convinced.

Goudsmit met once more with Thomas, but the case was finally settled. The formulae fit the atomic spectra, full derivations were provided, and were introduced, and a new

interpretation of the hydrogen spectrum was given. Thomas informed Goudsmit that over a year prior, Kronig had presented a similar idea to Pauli regarding a spinning electron, but Pauli ridiculed the work and it reached no further result. Even so, Kronig was not the first. Compton speculated on the idea of a spinning electron. In neither Comptons nor Kronigs case were the current interpretations of the hydrogen spectrum or the and quantum numbers available,

and their results they achieved were few and ultimately erroneous. [3] The final result published by Goudsmit and Uhlenbeck contains a very fitting model to describe previously misunderstood phenomena in spectroscopy. The circumstances surrounding this final discovery are remarkable; yet nature often reveals its secrets in surprising ways to those who seek understanding, and sometimes by using sources that bring mankind a necessary humility in the face of all our seemingly vast knowledge.

Works Cited

[1] D.J. Griffiths, Introduction to Quantum Mechanics, (Prentice Hall, New Jersey, 2005), 2nd ed. [2]
McMurry, John, and Robert Fay. Chemistry. 6th. Upper Saddle River: Pearson Prentice Hall, 2012. 161162. Print.

[3]
van der Waals, J.H.. "The Discovery of Electron Spin." . N.p.. Web. 26 Apr 2013. <http://www.lorentz.leidenuniv.nl/history/spin/goudsmit.html>.