Pauli, an ergodic theorem and related matters

Peter T. Landsberga)
School of Mathematics, University of Southampton, Southampton SO17 12BJ, United Kingdom

Received 6 July 2004; accepted 10 September 2004 Time averages are important in physics and in statistical mechanics. An ergodic theorem is a way of justifying the replacement of time averages by averages in phase space. A derivation of this theorem from quantum mechanics was given by von Neumann in 1929. Pauli and Fierz found a shorter argument in 1937. They agreed that for ergodicity to hold there should be no energy degeneracy in the Hamiltonian. I trace the circumstances and consequences of a disproof of these arguments. 2005 American Association of Physics Teachers. DOI: 10.1119/1.1811622

I. INTRODUCTION This paper is about a fairly unknown development in the history of physics but it involves famous people, notably John von Neumann and Wolfgang Pauli. I apologize that it is also about me, but that is essential for me to be able to tell you this story!1 The literature about the ergodic theorem is complicated, but one can say that a system is ergodic if the time average of any quantity pertaining to a single system of interest agrees with the ensemble average for that quantity.2 The existence of ergodicity has also led to a huge literature in pure mathematics. Here we are more interested in its effect on quantum mechanics. The story started near the beginning of my university career in about 1950, and reached an end only in 2003, near the very end of my university career. It should be of wider interest, because it involves the famous scientists I have mentioned. Please do not be put off by the word theorem. A theorem can upset nonmathematicians, because they think of difcult proofs of theorems they have come across in the past. We shall approach this story more simply. II. WHO WAS PAULI? Pauli burst upon the scientic scene when he published his Relativitaets theorie.3 Einstein later wrote,4 No one studying this mature, grandly conceived work would believe that the author is a man of twenty-one. One wonders what to admire most, the psychological understanding for the development of the ideas, the sureness of mathematical deduction, the profound physical insight, the capacity for lucid, systematic presentation, the knowledge of the literature, the complete treatment of the subject matter, or the sureness of critical appraisal. The early promise suggested by the relativity article was fullled soon after its publication. Already in 1924 Pauli produced his work on the exclusion principle for which he was awarded the Nobel prize in 1945. Later he proposed the existence of the neutrino as a particle which could presumably not be detected. It was nally found in 1956. Further, during his stay in Hamburg the Pauli effect was discovered. This effect implies that all experiments go wrong as soon as Pauli comes into the room. During his relatively short life, Pauli 19001958 became widely accepted as a successor of Einstein. Max Born said that5 ...ever since the time he had been my assistant in
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Gottingen, I had been aware that he was a genius, comparable only with Einstein himself. Indeed from the point of view of pure science, he was possibly even greater than Einstein, even if as an entirely different type of person he never, in my opinion, attained Einsteins greatness... .

III. THE ERGODIC AND H-THEOREMS OF STATISTICAL MECHANICS Here are the assumptions we need. One assumes that the system of interest can be in any one of a number of quantum states i 1,2,... These are the states of a simplied system in which the small interactions which cause transitions between these states are neglected. It is assumed that there are probabilities p i of nding the system in state i and that a statistical entropy function S(p 1 , p 2 ,...) exists and is expressible in terms of the p i only. In equilibrium the entropy function attains a maximum with respect to each p i . With these values for the p i one can reasonably take the equilibrium value of a quantity A, which has values A i in the state i, to be given by the average of A A i p i . The identication of this ensemble average with the time average of A represents the ergodic theorem. A system treated as classical will be said to be ergodic if time averages and phase space averages over the energy surface coincide at least approximately. This idea is fairly simple, although its proof in a specic case may be quite difcult. One can see that it is important for any system which consists of several particles because the time average behavior is what would interest us. Hence, it would be useful if one could replace the time average by a phase space average. The ergodic theorem implies that this replacement is possible for ergodic systems. The convenience arising from this hypothesis is obvious, and so it is desirable to nd under what conditions it holds. The subject became an important component of pure mathematics. For metrically transitive systems the energy surface cannot be divided into nite regions such that a trajectory starting in one region will stay in that region for all time. These systems satisfy the ergodic theorem. Unfortunately, it is difcult to decide if a system is metrically transitive. We will not here concern ourselves with this aspect of the work. Consider now the entropy expression S k i p i ln pi , which results from Shannons uniqueness theorem for the
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entropy.6 To derive it he used several important properties of the entropy. But he did not use the following result: For an adiabatically isolated system the entropy increases with time or stays constant . This is an important property of the entropy, and, because it was not used in its derivation, it appears now as a theorem. Indeed, it is essentially the content of the famous H-theorem, the history of which goes back to Boltzmann.2 IV. THE DENOUEMENT You will not nd the old arguments of von Neumann,7 Pauli and Fierz,8 and later expositions, for example, by George Uhlenbeck9 in modern books. These scientists are very famous, and you might wonder why their expositions are now neglected. The answer is surprising: they all attempted to expound a result that is essentially wrong. How is it that a wrong or misleading result had had such a good and long life 19291957 ? I am afraid that the answer must be that the various authors thought the result was reasonable. In addition, the people who established it had a great reputation. So their result was just accepted, but apparently never checked in detailpossibly because the arguments were just too involved. What does one expect is needed for ergodicity? I could but wont here give you a short plausibility argument that suggests that for ergodicity the system Hamiltonian must have eigenvalues which are all different, that is, the Hamiltonian must be nondegenerate. My argument is much simpler than that employed by von Neumann7 and by Pauli and Fierz8 and is also misleading! But at least it gives a hint at the main and erroneous! conclusion of these early authors that ergodicity requires nondegeneracy of the Hamiltonian. Indeed their argument required more, which my simple argument does not, namely that not only the energies but also the energy differences must all be different. This whole matter arose, as I have noted, at the beginning of my academic career which was at the University of Aberdeen. I had been asked to lecture on statistical mechanics, and my friend Dr. now Professor Charles McCombie claimed that you could not do statistical mechanics unless you rst discuss the ergodic theorem. This claim made sense to me and took me to the long and complex paper by von Neumann as well as to the paper by Pauli and Fierz. Von Neumanns paper was published in 1929,7 when he was only 26 years old, three years before his famous book on the mathematical foundations of quantum mechanics.10 The PauliFierz paper8 was published when Pauli was 37 years old. As I have mentioned, these papers were seriously awed, but I did not discover this upon rst reading of them. What I did discover was that because surely a system may still be ergodic if it exhibits a small number of degeneracies, one might have wanted to know how many degeneracies would still be acceptable. None of these papers dealt with this question and nobody writing in this area had raised it, let alone tried to nd an answer to it. It seemed to me an obvious problem for a Ph.D student, and this is how Ian Farquhar got involved. On allowing degeneracies of the Hamiltonian we found that the earlier arguments still went through. It is clear that no one had looked at this question, for it suggested using the ideas of Pauli and Fierz and von Neumann that degeneracies of the Hamiltonian had nothing whatever to do with ergod120 Am. J. Phys., Vol. 73, No. 2, February 2005

icity. Essentially the old theorems were dead. I will not go into the mathematics of this nding, as it would not help us here. What to do? von Neumann was already ill he died early in 1957 , and I felt that we could not simply publish our results. We had to get Paulis reaction rst. So we wrote a polite letter to Pauli asking for his opinion. Because I had published in the area of statistical mechanics before, I imagine my name was not completely unknown to him. Anyway, nothing was said about that, and indeed nothing happened for what seemed a long time, but in fact it was only about two or three months. Then we received a letter from Pauli, saying that both he and Fierz agreed with us, and he would be glad to communicate our paper to the Royal Society of which he was of course a foreign member . In those days publications in the Royal Society were always preceded by the name of the person who had communicated the paper. I do not know of any other paper that had Paulis name attached in that manner. Anyway, that was that!11 We turned our minds now to other things. Unanswered questions, however, were how Pauli and Fierz discussed this matter, what was said, etc., apparently now unobservable. We will, however, come to them next.12 V. THE PAULI LETTERS In February 2001 there appeared in the American physics journal Physics Today an article about Pauli by Karl von Meyenn and Engelbert Schucking.12 The former is the editor of Paulis scientic correpondence. Some time later, when I visited my cousin in Bern, it proved possible to have a pleasant meeting with von Meyenn. A little while later he told me that it appeared from a letter he found that Abraham Pais had asked Pauli about me with a view of possibly inviting me to Princeton. Returning to the edition of Pauli letters, there seem to be a staggering 3500 of these, of which von Meyenn estimates that, about two thirds were written by Pauli himself. In any case von Meyenn drew my attention to a Pauli letter of 9 August 1956 no. 2320 in Vol. IV, Part III addressed to Professor Fierz, in which he says my translation from the original German As far as assumption B is concerned ... This was a key assumption in the PauliFierz paper I consider it now not only as lacking in plausibility, but nonsense his emphases . The view of the gentlemen Farquhar and Landsberg about this assumption is not expressed as sharply as that, but I have the impression that they also do not believe in it. It apears to me almost that they are laughing at us Neumann, me, and you as the great masters ... . Here, then, I had at last a small hint at the nature of the PauliFierz discussion. It was Pauli who now realized the enormity of the error in the original von Neumann paper, and carried over into their own PauliFierz . I had no idea that such letters were exchanged in the several months during which we waited for Paulis reply to the letter which we sent to him in August 1956. VI. MORE RECENT IDEAS The subject of irreversibility made great strides in the second half of the last century.14,15 To trace this subject in any detail here is not really possible. Nonergodic systems exist of course. Thus the matrix of transition probabilities might decompose into blocks such that there are no transitions between different blocks. Such a system is clearly nonergodic. In an ergodic ow system the phase space volume changes in
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shape but not in size, and after a long time all domains are reached by the phase point. Also possible are ows, such as can be exhibited by a hard sphere gas, which can develop fractal shapes. These and similar ows are possible and would require several lectures to elucidate.

ACKNOWLEDGMENT The author is grateful to Professor C. W. McCombie, Reading, for comments on the manuscript.
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Electronic mail: ptl@soton.ac.uk This article is based on a talk given by the author at the University of Bristol in June 2004. 2 R. C. Tolman, The Principles of Statistical Mechanics Oxford U.P., New York, 1938 , pp. 472 474. 3 W. Pauli, Die Relativitatstheorie, Enc. d. math. Wiss. 5, 698 1921 Leipzig, Teubner . 4 A. Einstein, Naturwiss 10, 184 185 1922 . 5 M. Born, The Born-Einstein Letters Macmillan, London, 1971 , p. 221.
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C. E. Shannon and W. Weaver, The Mathematical Theory of Communication University of Illinois Press, Urbana, 1963 . 7 J. von Neumann, Beweis des Ergodensatzes und des H-Theorems in der neuen Mechanik, Z. Phys. 57, 3037 1929 ; N. Macrae, John von Neumann Pantheon, 1992 . 8 W. Pauli and M. Fierz, Uber das H-Theorem in der Quantenmechanik, Z. Phys. 106, 572587 1937 . 9 G. E. Uhlenbeck, Problems of statistical physics, in The Physicists Conception of Nature, edited by J. Mehra Reidel, Dordrecht, 1973 . 10 J. von Neumann, Mathematical Foundations of Quantum Mechanics Princeton U.P., New York, 1932 . 11 E. Farquhar and P. T. Landsberg, The quantum-statistical ergodic and H-theorems, Proc. R. Soc. London, Ser. A 239, 134 144 1957 . 12 Karl von Meyenn and Engelbert Schucking, Wolfgang Pauli, Phys. Today 55 10 , 42 46 2002 . 13 W. Pauli, Writings on Physics and Philosophy, edited by Charles P. Enz. and Karl von Meyenn, translated by Robert Schlapp Springer-Verlag, Berlin, 1994 . 14 M. Fierz, Statistische Mechanik, in Theoretical Physics in the Twentieth Century A Memorial Volume to Wolfgang Pauli Interscience, New York, 1960 . 15 B. Bernstein and T. Erber, Reversibility, irreversibility: Restorability, non-restorability, J. Phys. A 32, 75817602 1999 .

Edison Cell. In the rst years of the 20th century, Thomas A. Edison and his staff worked on the development of a useful storage battery to power electric automobiles. The resulting nickel-iron battery, with a sodium/lithium hydroxide electrolyte, produced about 1.2 V and was more efcient per unit weight than contemporary lead-acid storage batteries. After the demise of the electric car, the batteries were widely used in scientic work because they had a low internal resistance, and so gave a steady voltage output almost to the end of the charging cycle. This pair of cells is in the Greenslade Collection. Photograph and notes by Thomas B. Greenslade, Jr., Kenyon College

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