Max Planck and the Birth of the Quantum Hypothesis

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Max Planck and the birth of the quantum hypothesis Michael Nauenberg Department of Physics, University of California, Santa Cruz, California 95060 (Received 25 August 2015; accepted 14 June 2016) Based on the functional dependence of entropy on energy, and on Wien’s distribution for black- body radiation, Max Planck obtained a formula for this radiation by an interpolation relation that ﬁtted the experimental measurements of thermal radiation at the Physikalisch Technishe Reichanstalt (PTR) in Berlin in the late 19th century. Surprisingly, his purely phenomenological result turned out to be not just an approximation, as would have been expected, but an exact relation. To obtain a physical interpretation for his formula, Planck then turned to Boltzmann’s 1877 paper on the statistical interpretation of entropy, which led him to introduce the fundamental concept of energy discreteness into physics. A novel aspect of our account that has been missed in previous historical studies of Planck’s discovery is to show that Planck could have found his phenomenological formula partially derived in Boltzmann’s paper in terms of a variational parameter. But the dependence of this parameter on temperature is not contained in this paper, and it wasﬁrst derived by Planck. VC 2016 American Association of Physics Teachers. [http://dx.doi.org/10.1119/1.4955146]

I. INTRODUCTION of black-body radiation known as the ultraviolet catastrophe; this occurs when the equipartition theorem for a system in One of the most interesting episodes in the history of sci- thermal equilibrium is applied to the spectral distribution of ence was Max Planck’s introduction of the quantum hypoth- thermal radiation. But at the time, Planck appears to have esis, at the beginning of the 20th century. The emergence of been unaware of this problem, which was named by this revolutionary concept in physics is a fascinating story Ehrenfest several years after Planck’s discovery. Indeed, the 1–12 that has been described previously, but important aspects application of the equipartition theorem to black-body radia- of this discovery are generally not found in the description of tion was made by Lord Rayleigh17 at about the same time Planck’s ideas in physics textbooks that discuss quantum that Planck obtained his famous formula for the black-body mechanics. In particular, most physics textbooks do not men- spectrum. There isn’t any evidence that Planck was aware of tion how the concept of discreteness in energy, the revolu- Rayleigh’s result, which agreed with new experiments for tionary concept introduced by Planck to describe the the long wavelength end of the spectrum observed at that spectrum of black-body radiation, originated in thefirst time. Klein concluded that:3 place.8 From Planck’s articles and correspondence on his theory of the spectrum of black-body radiation, it is clear “it was probably a very good thing that Planck was that he took this concept directly from Boltzmann, who in not constrained in his thinking by the tight his seminal 1877 paper on statistical mechanics discretized classical web which Rayleigh had woven.” energy as a purely mathematical device in order to be able to In Boltzmann’s 1877 paper, the mean energy of hisfictitious count the possible configurations of a molecular gas in ther- molecular ensemble with discrete energies in multiples of a 13 mal equilibrium. But this important connection between unit is obtained in terms of an undetermined variational pa- Planck’s and Boltzmann’s work has not been mentioned rameter, but he calculated the temperature dependence of even in physics textbooks that emphasize a historical this parameter only in the limit relevant to classical mechan- 14 approach. For example, in the description of Planck’s dis- ics. It has remained unnoticed that his result corresponds to covery in his biography of Einstein, Abraham Pais concludes Planck’s formula for the black-body radiation spectrum (see 15 that: Ref. 13, p. 181, and Appendix A). “His [Planck’s] reasoning was mad, but his In essence, Planck’s approach to the theory of black-body madness has that divine quality that only the radiation was based on the following steps. Taking advant- greatest transitional figures can bring to science.” age of Kirchhoff’s theorem that the black-body distribution is a universal function independent of the nature of the This comment does not provide any more enlightenment on source of radiation, Planck’sfirst step was to obtain a rela- the origin of the idea of quantization in physics than Richard tion for the energy distribution of this radiation in thermal Feynman’s succinct statement in his well-known Lectures on equilibrium with an ensemble of microscopic Hertzian oscil- Physics, that:16 lators with variable frequency. By applying Wien’s distribution thatfitted the high frequency end of this radiation, “…by fiddling around [Planck] found a simple and Maxwell’s equations for the electromagneticfield, derivation [for his formula].” Planck obtained an expression for the mean energy of these Most accounts of Planck’s discovery in physics textbooks oscillators. The measurements were made by careful experi- are historically inaccurate, and Martin Klein’s early analysis ments at the Physikalisch Technische Reichanstalt (PTR), of Planck’s work3 debunked some myths contained in these which was the center for infrared radiation studies in Berlin books. For example, one of the most common myths is that at the end of the 19th century (see Fig. 1). After it was dis- Planck was responding to the problem in the classical theory covered that Wien’s distribution did notfit new data at lower

709 Am. J. Phys. 84 (9), September 2016 http://aapt.org/ajp VC 2016 American Association of Physics Teachers 709

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 Fig. 1. Apparatus of Lummer and Kurlbaum to measure the spectrum of black-body radiation. An electrical current heats theﬁlamentE located in a tube inside the cylinderC to aﬁxed temperatureT, giving rise to black-body radiation inside this cylinder. The spectrum of this radiation is observed by some radiation exiting through the hole at one end along the axis of the cylinder.

frequencies, Planck obtained a new distribution formula by h, where is the frequency of his oscillators andh is a an interpolation based on his application of the relationship new¼ universal constant, now known as Planck’s constant, between entropy and energy for a system in thermal equilib- that relates frequency and energy. It was very fortunate for rium. Finally, to obtain a theoretical interpretation for his Planck that Boltzmann initially considered energy as the new formula, Planck turned to the seminal 1877 paper of only degree of freedom of the molecules in his ensemble Boltzmann, which formulates the relation between entropy because that made possible Planck’s direct extension to an and statistics.13 ensemble of linear harmonic oscillators.18 In his paper, Boltzmann introduced a relation between the Planck was aware that with his procedure he was violating entropy of a molecular gas and the number of microscopic the tenets of continuum physics. In his December 19, 1900 configurations, or complexions (as he called them), of the paper, presented at a meeting of the German Physical molecules. He defined the state of thermal equilibrium to be Society, he wrote that:19 the maximum number of these configurations subject to the “IfE [the total energy] is considered to be a constraint of afixed number of molecules and total energy. continuous divisible quantity this distribution is Atfirst sight, it is surprising that Boltzmann’s ideas, based possible in infinitely many ways. We consider, on purely classical concepts applying to systems having con- however—this is the most essential point of the tinuous energy, could have served as the springboard for whole calculation—E to be composed of a well- Planck’s quantum hypothesis of discrete energy levels. But defined number of equal parts [of magnitude] to implement his statistical ideas, Boltzmann took for his ini- and use thereto the constant of natureh tial example afictitious model of a gas, whose molecules 27 ¼ 6:55 10 erg sec [setting h].” had discrete energies in integer multiples of an energy ele- ¼ ment of magnitude. For Boltzmann, this discretization of There were, however, inconsistencies in Planck’s introduc- energy was purely a mathematical artifact that he introduced tion of discrete energy for his Hertzian oscillators because in for the purpose of counting the number of configurations of his derivation of the relationship between the black-body the molecules. Subsequently, as would be expected, he took energy spectrum and the mean energy of these oscillators, the limit of continuous molecular energy for which van- Planck applied continuum mechanics and Maxwell’s equa- ished. But when Planck applied Boltzmann’s discrete model tions for electromagnetism. For example, an obvious question to his ensemble of Hertzian oscillators in thermal equilib- would have been to explain how Planck’s oscillators could be rium with radiation, he did not take this continuum limit. restricted to discrete energies while changing energy by emit- Instead, he set Boltzmann’s energy elements to afixed value ting and absorbing electromagnetic waves in a continuous

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This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 manner. This problem did not affect Boltzmann because he “While a host of outstanding physicists worked on could assume that initially his molecules transfer energy in the problem of spectral distribution, both from the discrete units, but in the end, he took a continuum limit. experimental and the theoretical aspects every one of Many years later, Einstein commented that:20 them directed his efforts solely toward exhibiting the dependence of the intensity of the radiation on the “…all my attempts…to adapt the theoretical temperature. On the other hand, I suspected that the foundations of physics to the edge failed fundamental connection lies in the completely. It was as if the ground had been pulled dependence of [my italics]. As the significance from under one, with no firm foundation to be seen entropy upon energy of entropy had not yet come to be fully appreciated, anywhere.” nobody paid any attention to the method adopted by In 1905, however, he resolved the conundrum by assuming me, and I could work out my calculations completely that electromagnetic radiation also consisted of discrete at my leisure, with absolute thoroughness, without energy quanta.21 But Planck did not show such concern, and fear of interference or competition. Since for the instead, for several years he attempted to incorporate his new irreversibility of the exchange of energy between an results within the realm of continuum classical physics. oscillator and the radiation activating it, the second Taking again another idea from Boltzmann’s 1877 paper, differential quotient of its entropy with respect to its Planck later considered the energy of the oscillator to be con- energy is of characteristic significance, I calculated tinuous, and h to be the magnitude of cells of equal the value of this function on the assumption that probability in¼ the phase space of the oscillators. Otherwise, Wien’s law of the Spectral Energy Distribution is the derivation of his formula proceeds in precisely the same valid—a law which was then in the focus of general form as before. In 1906, and again as late as 1909, he pre- interest; I got the remarkable result that on this sented his derivation in lectures that he gave during his visit assumption the reciprocal of that value, which I shall at Columbia University. But had Planck closely followed call hereR, is proportional to the energy.” Boltzmann’s statistical method, he could have realized ear- 26 lier that a continuum energy interpretation of his formulae On theoretical grounds, Wien had proposed that the was not feasible. In a card to Ehrenfest in the spring of 1915, spectral energy distribution for black-body radiation with Planck wrote, “I hate discontinuity of energy even more than frequency at temperatureT had the scaling form discontinuity of emission.” q ;T 3f =T ; (1) The main purpose of this paper is to clarify the relationship ð Þ¼ ð Þ between Boltzmann’s and Planck’s work by providing a thor- wheref is a function of a single variable, the ratio of fre- ough mathematical discussion that is often absent in the litera- quency, and temperatureT. This form satisfies the Stefan- ture on this subject. In the following Secs. II–IV, Planck’s Boltzmann relation that the total black-body energy is pro- work is discussed as described in some of his publications, his portional to the fourth power of the temperatureT. autobiographical recollections,22 his Nobel speech,23 and in Originally, this dependence was found experimentally by some of his correspondence. Section II reviews Planck’s origi- Josef Stefan, and later a theoretical derivation was provided nal serendipitous derivation of his well-known formula for in 1884 by his former student Boltzmann.27 Boltzmann’s black-body radiation, which he referred to as his “lucky method was succinct: applying Maxwell’s relation between intuition.” Section III describes his application of the energy per unit volumeE, and the pressurep of isotropic Boltzmann’s principles of statistical mechanics, and Sec. IV radiation, =3 leads to a relation for the entropy per describes some of Planck’s recollections on how he discov- p E S R unit volume¼ of this radiation ered his fundamental radiation formula. The relationship between Boltzmann’s work and Planck’s application of it is 4 E given in Appendix A, which also contains some new mathe- SR : (2) ¼ 3 T matical insights concerning this relation. Finally, Appendix B discusses some of the controversies among historians of sci- Substituting for the temperatureT in this relation the thermo- ence about Planck’s role in the introduction of the quantum. dynamic condition 1 dS II. PLANCK’S PHENOMENOLOGICAL R ; (3) DERIVATION OF HIS BLACK-BODY FORMULA T ¼ dE An insightful description of how Planck obtained his fa- and integrating the resulting differential equation yields 3=4 mous formula for the spectrum of black-body radiation can SR c 0E . EliminatingS R by applying again Eq. (2), one 22 be found in his scientific autobiography. This account was obtains¼ the relationE rT 4, known as the Stefan- ¼ 4 written many years after the occurrence of this event, and Boltzmann law, wherer 3c 0=4 is a universal constant. may suffer from the usual lapses of memory and the absence According to Wien’s¼ð spectral distributionÞ in Eq. (1), inte- of original documents and correspondence. Planck’s own grating the spectrum over all frequencies and settingz papers and correspondence were destroyed when Berlin was =T as the variable of integration, one recovers the Stefan-¼ bombed in WWII. It appears, however, to be consistent with Boltzmann relation Planck’s original publications. Therefore, here Planck will ð speak for himself, while, for clarification, some of the mathe- 1 E q ;T d rT 4; (4) matical details will befilled in (keeping his original notation) ¼ 0 ð Þ ¼ in a form close to his original articles. Planck wrote:22 wherer is now determined by

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This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 ð 1 3 Integrating this equation with the boundary condition thatS r z f z dz: (5) vanishes whenU 0 gives ¼ 0 ð Þ ¼ U U Probably stimulated by earlier phenomenological work by S ln 1 : (11) Paschen, Wien assumed for the functionf z the exponential ¼ b a form ð Þ In the last of a series offive papers by Planck on irreversible 29 8pa bz radiation processes, this expression appears, without any f z e ; (6) ð Þ ¼ c3 justification, as a definition for the entropy of his oscillators. But as has been shown, it is clear that Planck obtained it in a wherea andb are constants that could be obtained byfitting straightforward fashion from Wien’s relation of Eqs. (1) and his theoretical distribution of Eq. (1) to the black-body radia- (6).31 Taking the second derivative ofS with respect toU, he tion experiments. The constanta has the dimensions of found that its reciprocal depends linearly onU or energy time and later it will be seen to correspond to 1 Planck’s constanth. For this form off, according to Eq. (5), d2S 4 3 R bU: (12) r 48pa=b c . ¼ dU2 ¼ ¼Subsequently, in a series offive papers written between 1897 and 1899, Planck discussed the thermal equilibrium While Planck obtained this simple linear dependence ofR on between the radiation in a cavity and an ensemble of Hertzian U from Wien’s relation, he attached to it a special signifi- 28,29 electromagnetic oscillators, based on Maxwell’s theory of cance claiming to have demonstrated that it was unique, electromagnetism. His main result was a relation between the leading to a derivation of the scaling dependence ofU ;T spectral distributionq ;T and the mean energyU ;T of on and , Eq. (8). Integrating this equation gives ð Þ ð Þ ð Þ T the oscillators dS 1 U 8p ln ; (13) q;T 2U;T : (7) dU ¼ b n ð Þ ¼ c3 ð Þ ð Þ wheren is an undetermined function of. Hence, the fact Combining this result with Wien’s relation, Eqs. (1) and (6), that Wien’sð Þ relation indicates thatn depends linearly on implies that was not justified. ð Þ In a paper presented to the Berlin Academy of Sciences on b=T 32 U ;T ae : (8) May 18, 1899, Planck stated that: ð Þ¼ “I believe it must therefore be concluded that the In this expression, the constanta (which, like Wien’s corre- definition given for the entropy of radiation, and also sponding constanta) has the dimensions of energy times the Wien distribution law for the energy which goes time and turns out to be equal to Planck’s constanth. Byfit- with it, is a necessary consequence of applying the ting the data on blackbody radiation obtained in the experi- 30 principle of entropy increase to the electromagnetic ments by Otto Lummer and Ernst Pringscheim on radiation theory of radiation, and that the limits of validity of emitted from a small hole in a heated cavity (see Fig. 1), 27 this law, should there be any, therefore coincide with Planck obtainedh 6:88510 erg s, in remarkable corre- ¼ 27 those of the second law of thermodynamics. Further spondence to the modern valueh 6:62610 ergs, a trib- ute to the accuracy of the black¼ body radiation experiments experimental test for this law naturally acquires all at that time. Neither Wien, Planck, nor anyone else seemed the greater fundamental interest for this reason.” to notice, however, until it was pointed out by Lord Rayleigh Later on in his autobiography, Planck recalled that:22 several years later,17 that the Wien exponential law, Eq. (6), implied the implausible result that as the temperatureT “This relationship is so surprisingly simple that for a increases the magnitude of the spectral distribution at afixed while I considered it to possess universal validity, and I endeavored to prove it theoretically. However, frequency approaches a constant valueq ;T 8ph 3=c3, andU h, independent ofT. ð Þ¼ this view soon proved to be untenable in the face of Planck’s¼ next step was to consider the dependence of the later measurements. For although in the case of entropyS ;U of his oscillators on the energyU. Given the small energies and correspondingly short waves relation betweenð Þ the energyU and the temperatureT [of Eq. Wien’s Law continued to be confirmed in a (8)], he obtained this dependence from the thermodynamic satisfactory manner, in the case of large values of the relation energy and correspondingly long waves, appreciable divergences were found, first by Lummer and 1 dS Pringsheim; and finally the measurements of H. : (9) Rubens and F. Kurlbaum on infrared rays of T dU ¼ fluorspar and rock salt revealed a behaviour which, Inverting Eq. (8) to obtainT as a function ofU, and substitut- though totally different, is again a simple one, in so ing the result in Eq. (9), gives afirst-order differential equa- far as the function R is proportional not to the energy tion forS: but to the square of the energy for large values of the energy and the wave-lengths.” dS 1 U ln : (10) By early 1900, the experiments of Otto Lummer and Ernst dU ¼ b a Pringscheim30 gave evidence of deviations from Wien’s

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This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 formula at the longer observed wavelengths of order 10lm, he obtained his previous linear dependence ofR onU, Eq. 33 and at temperature of about 1000 C. Further data by (12), forU gb and the quadratic dependence onU, Eq. Heinrich Rubens and Felix Kurlbaum at a wavelength of (16), forUgb. This simple interpolation formula forR 51lm indicated that the black body radiation depends line- turned out, surprisingly, to be valid not only in these two arly on temperature.34 These experiments were made possi- energy regimes, but to be an exact relation for all values of ble by a new detection technique developed by Heinrich U. Integrating this relation by applying the thermodynamic Rubens and his American collaborator Ernst F. N. Nichols, relation between the absolute temperature and the derivative which enhanced the low intensity longer wavelengths by res- of the entropy with respect to the energy [Eq. (9)], and onant scattering from a crystal lattice.35 Planck was informed assuming the boundary conditionU whenT , of these new results by Rubens himself, who visited him one obtains !1 !1 with his wife on a Sunday afternoon (Oct. 7, 1900), and he began promptly to reconsider his arguments. 1 1 ln 1 gb=U ; (18) Even before the new data appeared, Lord Rayleigh derived T ¼ b ðþ Þ a linear dependence on temperature for the blackbody distribution from the equipartition theorem, applied to classical which yields the dependence on temperatureT and frequency radiation emitted by charged one-dimensional oscillators in a of the mean oscillator energy box in thermal equilibrium.17 To obtain this dependence on temperature, Planck found that his expression forR of Eq. gb 28 U;T : (19) (12) had to depend quadratically onU. Supposing that ð Þ ¼ expb=T 1 ð Þ U ;T gT; (14) ð Þ¼ Finally, to recover the relation forU ;T in the Wien limit when , Planck obtained a relationð Þ for the new con- where is a constant (named in Planck’s paper and corre- b T g a stant : sponding tok), then according to Eq. (9) g

1 dS g h ; (15) g : (20) T ¼ dU ¼ U ¼ b and therefore Sinceb h=k, wherek is Boltzmann constant,g k in ¼ ¼ accordance with the equipartition theorem for a one- 1 d2S U2 dimensional harmonic oscillator. Substituting this expres- R : (16) sion into Eq. (7) for his relation between the spectral ¼ dU2 ¼ g distributionq ;T and the mean oscillator energyU ;T , ð Þ ð Þ In Planck’s own words,22 Planck then obtained his blackbody formula which he wrote as a function of the wavelengthk measured in the experi- “Thus, direct experiments established two simple ments28 as limits for the function R: for small energies, R is proportional to the energy; for larger energy values 5 Ck R is proportional to the square of the energy. q k;T ; (21) ð Þ ¼ exp bc=kT 1 Obviously, just as every principle of spectra ð Þ energy distribution yields a certain value for R, so whereC 8phc;k c=, andc is the velocity of light. In also every formula for R leads to a definite law of ¼ ¼ the distribution of energy. The problem was to find the limit bc=k T, Planck recovered his earlier result for the Wien spectrum, Eq. (6), while for bc=k T, he obtained such a formula for R which would result in the law of the distribution of energy established by the linear dependence ofq onT, in accordance with the new measurement. Therefore, the most obvious step for experimental results at the PTR. It should be pointed out that the general case was to make the values of R equal it is completely unexpected that by an interpolation proce- to the sum of a term proportional to the first power dure toﬁt experimental data Planck obtained a formula for of the energy and another term proportional to the the spectral distribution of black body radiation that turned second power of the energy, so that the first term out to be exact for all temperatures and wavelengths. His becomes decisive for small values of the energy procedure was sensible as a phenomenological dataﬁtting and the second term for large values. In this way a approach, but it is purely accidental that he succeeded in this new radiation formula was obtained, and I way to obtain the exact formula for black-body radiation. submitted it for examination to the Berlin Physical After all, he did not have any arguments to exclude, for Society, at the meeting on October 19, 1900.” example, cubic or higher powers ofU in his expansion ofR in powers ofU [Eq. (17)]. By such phenomenological considerations, Planck gener- After Rubens checked the new radiation formula against alized his thermodynamic expression for the dependence of his experiments, Planck described his reaction:22 the entropy on the oscillator energy to interpolate between the short wavelength or Wien regime, and the long wave- “The very next morning I received a visit from my length or Rayleigh regime. Setting now colleague Rubens. He came to tell me that after the conclusion of the meeting, he had that very night 1 checked my formula against the results of his d2S 1 R Ugb U ; (17) measurements and found a satisfactory concordance ¼ dU2 ¼ g ðþ Þ at every point …Later measurements too confirmed

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This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 my radiation formula again and again—the finer the forW, which is obtained whenS is replaced by its methods of measurement used, the more accurate value corresponding to the above radiation law the formula was found to be. …In this way a new could be interpreted as a measure of probability.” radiation formula was obtained, and I submitted it By integrating Eq. (18), with the boundary condition that the for examination to the Berlin Physical Society, at entropyS vanishes whenU 0, Planck obtained the meeting of October 19, 1900.” ¼ Planck, however, did not refer to Rayleigh’s result, whose S k 1 U=h ln 1 U=h U=h ln U=h ; ¼ ½ð þ Þ ð þ Þð Þ ð Þ work was apparently motivated by the unphysical depend- (22) ence of Wien’s formula that predicted the spectral energy q k;T saturates whenkT hc=k. To this Rayleigh wherek h=b is Boltzmann’s constant. This form of the de- ð Þ 17 remarked, pendence¼ ofS onU and satisfies the Wien’s scaling rela- “Nevertheless, the [Wien’s] law seems rather tion [Eq. (1)], indicating thatS depends only on the ratio difficult of acceptance, especially the implication U=. that as the temperature is raised, the radiation of Having found a phenomenological expression for the en- given wavelength approaches a limit…The tropyS as a function of the mean energyU, Planck considered the possibility that the functionW exp S=k could be question is one to be settled by experiment; but in ¼ ð Þ the meantime I venture to suggest a modification interpretated as a measure of the probability for the configu- of the Wien distribution, which appears to me ration of his Hertzian oscillators, corresponding to that of molecular velocities in Boltzmann’s 1877 formulation of sta- more probable apriori. Speculations upon this tistical mechanics.13 In his Nobel speech,23 Planck subject are hampered by the difficulties which remarked, attend the Boltzmann-Maxwell doctrine of the partition of energy [my italics]. According to this “As a result, I found that this was actually possible, doctrine every mode should be alike favoured; and and that in this connectionk represents the so-called although for some reason not yet explained the absolute gas constant, referred not to gram mole- doctrine fails in general, it seems plausible that it cules or mols, but to the real molecules. Now for applies for the graver [longer wavelengths] the magnitudeW, I found that in order to interpret it modes.” as a probability, it was necessary to introduce a universal constant, which I calledh. Since it had the dimension of action energy time , I gave it the III. PLANCK’S APPLICATION OF BOLTZMANN’S name elementary quantum½ of action . Thus the na- RELATION BETWEEN ENTROPY AND ture of entropy as a measure of probability, in the PROBABILITY IN STATISTICAL MECHANICS sense indicated by Boltzmann, was established in This section reviews the critical phase, when in order to the domain of radiation, too.” find the physical significance for his purely phenomenologi- Further evidence for Planck’s train of thought can be cal formula for black-body radiation of Eq. (21), Planck found in one of the few surviving letters from that period, turned to Boltzmann’s 1877 seminal paper on the founda- which he wrote to Otto Lummer on 26 October 1900,24 tions of statistical mechanics for enlightenment. Later, as Planck described it in his autobiography,22 “If the prospect should exist at all of a theoretical derivation of the radiation law, which I naturally “But even if the absolute precise validity of the assumed, then in my opinion, this can be the case radiation formula is taken for granted, so long as it only if it is possible to derive the expression for the had merely the standing of a law disclosed by probability of a radiant state, and this, you see, is lucky intuition, it could not be expected to possess given by the entropy. Probability presumes disorder, more than a formal significance. For this reason, and in the theory I have developed, the disorder on the very day when I formulated this law, I occurs in the irregularity with which the phase of the began to devote myself to the task of investing it oscillations changes even in the most homogeneous with a true physical meaning. This quest, as a light. A resonator, which corresponds to a matter of course, led me to study the interrelation monochromatic radiation, in resonant oscillations of entropy and probability—in other words to will likewise show irregular changes of its phase pursue the line of thought inaugurated by [and also of its instantaneous energy, which was Boltzmann [my italics].” more important for Planck’s subsequent derivation], 23 and on this the concept and magnitude of its entropy In his Nobel speech, Planck added the remark, are based. According to my [blackbody radiation] “After a few weeks of the most strenous work of formula communicated on 19 October to the my life, the darkness lifted and an unexpected German Academy] the entropy of the resonator vista began to appear.” should become and continued, b U U S a ln b U þ =U ; (23) “Since the entropyS is an additive magnitude, but ¼ ½ð þ Þ the probabilityW is a multiplicative one, I simply postulated thatS k logW, wherek is a universal and this form very much recalls expression occur- constant; and I¼ investigated whether the formula ring in the probability calculus.”

714 Am. J. Phys., Vol. 84, No. 9, September 2016 Michael Nauenberg 714

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 The equation that Planck wrote for the entropyS in this letter for a gas of molecules. He subsequently reinstated the classi- corresponds to Eq. (22) forb h, apart from an additive cal energy continuum by taking the limit 0. Planck fol- constant ab lnb, where ab k.¼ Planck continued, 24 lowed Boltzmann’s approach by assigning¼ integral multiples ¼ of these discrete energy elements to his oscillators of fre- “After all, in the thermodynamic of gases, too, the quency, but then departed from him in a fundamental way entropy is the log of a probability magnitude, S byfixing to have a constant value, h, whereh is a and Boltzmann has already stressed the close ¼ v new universal constant, instead of letting become vanish- relationship of the functionv which enters the ingly small as demanded by classical physics. Why Planck theory of combinatorics, with the dynamic did not take this latter step ( 0) is obvious: the assump- entropy. I believe, therefore, that the prospect tion of a discrete energy element! of magnitudeh gave him would certainly exist of arriving at my formula by precisely the result he was searching for to justify his phe- a theoretical route which would also give us the nomenological black-body formula. But as would be physical significance of the constantsC andc.” expected, he did not—and could not—justify such discrete- To illustrate his statistical principles for thermal equilib- ness on a priori grounds. It appears that in the short time rium, Boltzmann had considered a gas of molecules and in before Planck submitted his paper to the German Physical order to count the number of configurations or complexions, Society, he could not have been aware of the broader physi- as he called them, he discretized the energy of the molecules cal implications of his unprecedented ansatz because he did in integral multiples of a unit or energy element. Then each not offer any comments indicating that he was departing configuration is specified by a set of integers giving the num- from the canons of classical physics. Planck turned to ber of energy elements of each molecule subject to the con- Boltzmann’s approach rather late in his research program, straint that the mean energyU per molecule satisfies the and therefore it seems very likely that in 1900 he had not yet relationU P=N , whereP is an integer andN is the total fully mastered the foundation of Boltzmann’s statistical number of¼ð molecules.Þ It is fairly plausible, as indicated in his mechanics. letter to Lummer, that Planck started with his empirically suc- In this connection, it is interesting to examine Planck’s cessful relation for the entropyS of the oscillators of Eq. (22). own account of his discovery some 31 years later. In Then, working backwards, he proceeded to obtain the quantity response to a request from the American physicist Robert W exp S=k and associated it with the total number of con- Williams Wood, Planck described “the considerations which ¼ ð Þ led him to propose the hypothesis of energy quanta” in a let- figurations of his oscillators, in analogy with Boltzmann’s 25 model for a gas of molecules.2 In this case, replacing the ratio ter he wrote to him on October 7, 1931: U=h that appears in Eq. (22) forS byP/N, Planck would “Briefly summarized, what I did can be described as have obtained the relation simply an act of desperation. By nature I am peacefully inclined and reject all doubtful N P N P ðþ Þ adventures. But by then I had been wrestling W ðþ Þ ; (24) ¼ NNPP unsuccessfully for six years with the problem of the equilibrium between radiation and matter and I which is Stirling’s approximation to the total number of knew that the problem was of fundamental complexions given in Boltzmann’s paper. importance to physics; I also knew the formula that In two articles19,36 that he presented to the German expresses the energy distribution in the normal Physical Society, thefirst one given on Dec. 14, 1900, spectrum. A theoretical interpretation therefore had Planck now derived his entropy formula by starting with Eq. to be found at any cost, no matter how high. It was (24) for the total numberW of equally probable complexions clear to me that classical physics could offer no of his oscillators. He then obtained the entropyS from the solution to this problem and would have meant that relationS k logW by settingP=N U=h, which yields all energy would eventually transfer from matter Eq. (22).¼ In this presentation, Planck¼ introduced for thefirst into radiation [my italics]. In order to prevent this, a time the constantk h=b, and pointed out that it is universal new constant is required to assure that energy does and applies to¼ all thermodynamic systems including not disintegrate. But the only way to recognize how Boltzmann’s model for a gas of molecules. In this case,k this can be done is to start from a definite point R 0=N0 whereR 0 is the gas constant andN 0 is Avogadro’s of view. This approach was open to me by number.¼ Planck also argued that for each frequency, there maintaining the two laws of thermodynamics. The would be corresponding values ofN andP such that two laws, it seems to me, must be upheld under all P =N U =h and that the total number of configurations circumstances. For the rest, I was ready to sacrifice ¼ W (which is the product of allW ) should be maximized for every one of my previous convictions about physical afixed total energy, but he did not carry out such a laws. Boltzmann had explained how thermodynamic calculation. equilibrium is established by means of statistical equilibrium, and if such an approach is applied to IV. PLANCK’S 1931 RECOLLECTIONS the equilibrium between matter and radiation, one finds that the continuous loss of energy into In Sec. III, we have made a plausible reconstruction how radiation can be prevented by assuming that energy Planck obtained a theoretical derivation of his black-body is forced at the outset to remain together in certain formula based on Boltzmann’s development of statistical quanta. This was purely a formal assumption and I mechanics in 1877. The idea of introducing discrete energy really did not give it much thought except that no elements of magnitude originated with Boltzmann, who matter what the cost, I must bring about a positive applied it as a mathematical device to count configurations result.”

715 Am. J. Phys., Vol. 84, No. 9, September 2016 Michael Nauenberg 715

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 The statements in this letter agree with the description that (d) Finally, Planck took his “most essential step,” namely, can be gleaned from the papers and earlier correspondence to obtain a theoretical foundation for his new and suc- of Planck, but there are also some oddities in this account. cessful entropy and radiation formula. For this purpose, Contrary to Planck’s remark that “classical physics could Planck turned to Boltzmann’s 1877 paper on the con- offer no solution to this problem…” he continued to hope, nection of entropyS with the maximum number of for about a decade after hisfirst application of Boltzmann’s complexionsW B of a system in thermal equilibrium discrete statistical approach, that his quantum of action could (S lnW B). In particular, this paper contained an somehow be justified on purely classical grounds. As he expression/ for the total number of complexionsW for stated in his autobiography,22 an ensemble of one-dimensional molecules having multiples of a discrete energy element. Of course, “While the significance of the quantum of action since energy in classical mechanics is continuous, at for the interrelation between entropy and the end of his calculation Boltzmann took the limit probability was thus conclusively established, the 0, corresponding to the result of the equipartition part played by this new constant in the uniformly theorem,! first published for the distribution of black regular occurrence of physical processes still 17 body radiation by Lord Rayleigh. Planck, however, remained an open question. I therefore tried realized that by setting h, he recovered his suc- immediately to weld the elementary quantum of cessful phenomenological¼ relation for the entropy that action somehow into the framework of classical h led to his famous formula for the spectrum of black theory. But in the face of all such attempts, this body radiation. constant showed itself to be obdurate…” Klein3 and subsequently other historians of science have More likely, originally discreteness in energy for Planck questioned why Planck departed from Boltzmann’s deriva- was a “purely formal assumption” that Boltzmann had intro- tion by taking the total number of complexionsW instead of duced in 1877 to which Planck “really did not give much its maximum numberW B. The explanation is rather straight- thought” because it brought about “a positive result,” forward: Planck had obtained a phenomenological formula namely, a theoretical derivation of his black-body formula. for the entropy as the logarithm of a function of the variable Previously, this was obtained from phenomenological con- U=, with h [Eq. (22)]. Boltzmann’s paper, however, siderations by an adaptation of Boltzmann’s principles of did not contain¼ a corresponding expression for the entropy statistical mechanics to a model of oscillating charges in proportional to lnW as a function of this variable, except in thermal equilibrium with electromagnetic (black-body) radi- B the limit 0 (corresponding to classical mechanics). But ation. Planck’s good fortune was that these principles could his paper! contained an expression for the total number of be applied straightforwardly, not only to the systems in ther- complexionW in terms of the numberN of molecules, and modynamic equilibrium, which satisfy the laws of classical an integerP E=, whereE is the total energy of the sys- continuum physics, but also to the systems that are described tem. Substituting¼ P=N U=h in the Stirling approximation by discrete energy levels such as Hertzian oscillators in equi- forW leads to an expression¼ for ln W equal toN times librium with thermal radiation. Planck had been correct “to Planck’s phenomenological expressionð Þ for the entropyS uphold the two laws of thermodynamics under all circum- (apart from the constant of proportionalityk). It still stances” because, as it turned out, only these two laws were remained to be shown that lnW lnW B in the Stirling not modified by the advent of the new theory of quantum approximation, which was not carried¼ out in Boltzmann’s pa- mechanics. per (see Appendix A). In one of the most recent articles on this subject,4 Clayton Gearhart posed another question simi- V. SUMMARY AND CONCLUSIONS lar to that of other historians of science: “Why should Planck’s complexions, which represent distributions of The role of Planck in the introduction of the quantum hy- energy elements, be equally probable?” The answer is that pothesis has been described in numerous articles in the the assumption of equally probable complexions is at the past,1–12 and it turns out to be quite controversial (see foundation of Boltzmann’s statistical method, and naturally Appendix B). The account presented here has particularly Planck adopted it because it solved his problem. But for benefited from the articles by Rosenfeld,1,2 Klein,3 and Planck’s problem, this assumption was not justified because Gearhart.4 In summary, it has been shown here that: thermal equilibrium is due to the interaction of Planck’s (a) Assuming that the energy distribution for black body oscillators with radiation, which Planck assumed to follow radiation is due to an ensemble of Hertzian oscillators Maxwell’s continuous (not discrete) laws. A detailed discus- in equilibrium with this radiation at afixed temperature sion of the relation between Boltzmann’s and Planck’s defi- T, Planck calculated the relation of this distribution to nition and calculation of entropy is given in Appendix A. In the mean energy of these oscillators, Eq. (7), by apply- particular, it is shown that in the Stirling approximation, ing Maxwell’s theory of electromagnetism. lnW lnW B, an essential relation that Planck could have (b) On the basis of Wien’s displacement formula for this easily¼ demonstrated, but was not given in any of his papers. distribution, Planck then obtained an expression for the The occurrence of energy discreteness caused a great deal entropy of his Hertzian oscillators of Eq. (11). of concern to Planck’s contemporaries, most notably (c) Motivated by new experiments at longer wavelengths Einstein, Lorentz, and Ehrenfest, and it took several years that disagreed with Wien’s formula, Planck developed before the significance of Planck’s quantum of action began a phenomenological interpolation relation, Eq. (22), for to emerge. The acceptance and further development of his entropy relation that agreed very well with the new Planck’s hypothesis is a very interesting and important sub- and the older experiments. ject in its own right, but it will not be pursued here.

716 Am. J. Phys., Vol. 84, No. 9, September 2016 Michael Nauenberg 716

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 ACKNOWLEDGMENTS d lnW adn cdk 0: (A4) B þ þ ¼ The author would like to thank Clayton Gearhart for a In the Stirling approximation for the factorials that appear in careful reading of this manuscript and helpful comments, the expression forW in Eq. (A1), this expression becomes and the AJP reviewers for useful contributions. B Xp dn ln n a cj 0; (A5) APPENDIX A: THE RELATION BETWEEN j j j 0 ½ ð Þ þ þ ¼ BOLTZMANN’S AND PLANCK’S TREATMENT OF ¼

ENTROPY and settingn 0 exp a andx exp c , it is satisfied by ¼ ð Þ ¼ ð Þ An interesting question that has been raised by several his- j n n 0x : (A6) torians of science is to explain why Planck departed from the j ¼ method introduced by Boltzmann in his 1877 paper on the Substituting Eq. (A6) in Eqs. (A2) and (A3), and taking relation between the second law of thermodynamics and the 39 13 the limitp , we have theory of probability. In this paper, Boltzmann considered !1 the state of thermal equilibrium of an ensemble of molecules n j 1 x xj; (A7) having discrete energies that are multiples of an energy unit n ¼ ð Þ withfinite magnitude. Therefore, it would appear that by setting h, Planck could just have taken over for the fraction of molecules that have energyj, andx is Boltzmann’s¼ result for the mean energyU of these mole- determined by the ration=k, or cules, and shown that it corresponded to the result he had 1 obtained previously from his purely phenomenological con- x : (A8) siderations. It will be shown, however, that the reason why ¼ 1 n=k he could not have taken this apparently straightforward step þ is that Boltzmann had obtained the mean energyU of his This result was given explicitly by Boltzmann (Ref. 13, model for molecules with discrete energies in term of a pa- last line of p. 180) and leads to an expression for the mean rameterx, but he did not determine the dependence of this energyU k=n x= 1 x of the molecules in his en- ¼ ¼ ð Þ 40 parameter on temperature except in the classical limit when semble as a function ofx. Settingx exp b=T and ¼ ð Þ 0. He found in this case that , corresponding to h, this relation corresponds to Planck’s formula of Eq. U kT ¼ the! result of the classical equipartition¼ theorem.37 (19) for the mean energy of oscillators of frequency at the Boltzmann related the entropyS to the logarithm of the absolute temperatureT. But in his paper, Boltzmann did not calculate the dependence ofx onT. This dependence is maximum number of configurationsW B ofn molecules of fixed total energyk, wherek is an integer and the energy of obtained from Boltzmann’s identification of lnW B with the each molecule is a multiple of afixed value. In Sec. I of his entropyS of the system, by applying the second law of thermodynamics relation 1=T dS=dE. He did apply it only in paper, he gave an expression forW B associated with the dis- ¼ tribution ofk discrete energy elements of magnitude among the limit of vanishing appropriate to classical mechanics. Now we carry out this straightforward calculation forfi- n molecules such that a numbern j of molecules each have energyj, wherej 0;1;2;…;p, andp is an integer. Then nite. It would have been easy for Planck to do it too, but ¼ there isn’t any evidence that he did it. In the Stirling approximation, the maximum value of lnW as a function of Qn! B WB ; (A1) Boltzmann’s parameterx is ¼ nj! x and in terms of these variables, Boltzmann’s fundamental lnW B n lnx ln 1 x : (A9) principles of statistical mechanics can be stated as follows: ¼ 1 x ð Þ þ ð Þ Equally probable configurations (Boltzmann called them Substituting for its dependence on , we obtain complexions) are characterized by the set integersn j that are x n=k subject to the constraints that the total number of molecules n and the total energyE k arefixed, where lnW B n k ln n k n ln n k lnk; (A10) ¼ ¼ ð þ Þ ð þ Þ ð Þ p X which shows thatW B is the Stirling approximation for the n nj; (A2) total number of all possible complexionsW of Boltzmann’s ¼ j 0 ¼ ensemble (either of molecules or Planck’s oscillators), where

and n k 1 ! Xp W ðþ Þ : (A11) ¼ n 1 !k! k jnj; (A3) ð Þ ¼ j 0 ¼ Hence, the only puzzle is why Planck did not carry out this simple calculation that is missing in Boltzmann’s paper. wherep k because forj k,n j 0 or 1, and forj>k, n 0.38In this case, the¼ state of¼ thermal equilibrium is SettingU equal to the mean energy/molecule,U k=n, we j ¼ have, according to Eq. (A8) ¼ obtained by the maximum value of lnW B, subject to the constraints thatdn 0 and dk 0. Introducing two undeter- ¼ ¼ 1 mined constants,a andc (namedh andk by Boltzmann), this x ; (A12) condition is satisﬁed by the requirement that ¼ 1 =U þ

717 Am. J. Phys., Vol. 84, No. 9, September 2016 Michael Nauenberg 717

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 and substituting this expression into Eq. (A9), one obtains an claim originated with the appearance of Kuhn’s book and in 5 explicit dependence of lnWB onU his later article on this subject where he disputed the con- ventional view held by most physicists and earlier historians U U U U of science. For example, in his book, Kuhn concludes that lnW n1 ln 1 ln : (A13) B ¼ þ þ (Ref. 5, p. 126)

Apart from the constant of proportionalityk, this expression with h is equal ton times Planck’s phenomenological “With a single misleading exception, nothing in expression,¼ Eq. (22), for the entropy per oscillatorS Planck’s published papers, known manuscripts, or ¼ autobiographical fragments suggest that the idea of k lnW P of an ensemble of linear oscillators of frequency. ð Finally,Þ according to the second law of thermodynamics, restricting resonator energies to a discrete set of the absolute temperatureT for thermal equilibrium is given by values had even occurred to him as a possibility until others forced it upon him during 1906 and the 1 1 dS k years following.” ln 1 ; (A14) T ¼ n dU ¼ þ U Although some historians of science have criticized Kuhn’s which was calculated by Planck for h in Eqs. interpretation of Planck’s discovery, others have reached ¼ (18)–(20). Hence similar conclusions. While Kuhn agreed with many details in the traditional account of Planck’s work, he argued that cru- U ; (A15) cial aspects had been profoundly misinterpreted, and con- ¼ exp=kT 1 ð Þ cluded that energy quantization was actuallyﬁrst introduced by Einstein in 1906. and according to Eqs. (A12) and (A15), the dependence of Kuhn’s book was reviewed by the historians of science Boltzmann’s parameterx on the temperatureT is Klein,43 Peter Galison,44 Allan Needell,45 and by the physicist Res Jost,6 who were all critical of Kuhn’s thesis, but con- x exp =kT : (A16) 7 ¼ ð Þ clusions similar to Kuhn’s were reached by Oliver Darrigol, Substituting this expression into Eqs. (A6) and (A7) yields who even quoted Planck for “irrefutable evidence” that he had not meant to introduce energy discontinuities into physics, and later Greeenberg et al. also reached such con- nj n 1 exp =kT exp j=kT : (A17) ¼ ½ ð Þ ð Þ clusions.9 In 1984, Kuhn responded to some of his critics in an article defending his interpretation of Planck’s discovery But in theﬁrst section of his paper, Boltzmann did not calcu- 5 late this relation forn except in the limit that U, and of the quantum hypotheses by stating that j obtained “Part of the appeal of the standard account of Planck’s discovery is, I think, the closeness with n j which it matches a still cherished view of the nj exp ; (A18) U U nature of science and its developments. Although I appreciate both the charms and the functions of without giving the equipartition resultU kT of classical that view, understanding requires that it be ¼ thermodynamics (see Ref. 13, p. 186, and Ref. 38, p. 49). recognized as myth.” Settingj E; dE, andn j=n dp, thenp(E) is the Maxwell-Boltzmann¼ ¼ classical probability¼ distribution for Planck was aware that with his procedure he was violating Boltzmann’s molecular ensemble having energy in the inter- the tenets of continuum physics. In his Dec 19, 1900 paper, val betweenE andE dE presented at a meeting of the German Physical Society, he þ wrote:19 dp 1 exp E=U ; (A19) “IfE [the total energy] is considered to be a dE ¼ U ð Þ continuous divisible quantity this distribution is Ð 41 possible in infinitely many ways. We consider, with 1 , the mean energy/molecule. U 0 dE p E E however—this is the most essential point of the Boltzmann¼ pointedð out,Þ however, that this relation, with whole calculation—E to be composed of a well- 1 2 v 2, where is the mass andv is the velocity of a E = m m defined number of equal parts [of magnitude] molecule,¼ð Þ is valid only in two spatial dimensions.42 and use thereto the constant of natureh 27 ¼ 6:55 10 erg sec [setting h .” ¼ APPENDIX B: HISTORIAN’S DISAGREEMENT ON In view of this single remark, it is evident that Kuhn’s state- PLANCK’S ROLE IN THE INTRODUCTION OF THE ment quoted earlier that the “idea of restricting resonator QUANTUM energies to a discrete set of values had not even occurred to him [Planck]” is clearly incorrect. But as “irrefutable Since the publication of Kuhn’s 1978 book, Black-Body evidence” that Planck did not have energy discreetness in ,5 the nature of Theory and the Quantum Discontinuity mind, Darrigol has argued that Planck had remarked after- Planck’s discovery has become the subject of controversies 19 wards that among historians of science. Recently, some of them have claimed that contrary to what physicists have always been “If the ratio [E=] thus calculated is not an integer, led to believe, Planck did not introduce the concept of energy we take forP an integer in the neighbourhood of discreteness or quantization into physics.5,7 This surprising this ratio.”

718 Am. J. Phys., Vol. 84, No. 9, September 2016 Michael Nauenberg 718

This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 The assumption thatE= could not be an integer had to be 11J. Heilbron, “Nascent science. The scientific and psychological back- made by Boltzmann who considered that the magnitude ground to Bohr’s Trilogy,” in Love, Literature and the Quantum Atom becomes vanishingly small in the limit that the energy is a (Oxford U. P., 2013), Chap. 2.2. 12M. Badino, “The odd couple: Boltzmann, Planck and the application of continuous quantity, but not by Planck who considered as a statistics to physics (1900–1913),” Ann. Phys. (Berlin) 18, 81–101 (2009); fixed andfinite quantity equal toh. Moreover, Darrigol’s The Bumpy Road: Max Planck from Radiation Theory to the Quantum, comment is inconsistent with Planck’s previous statement (1896–1906) (Springer Briefs, 2015). thatE is “composed of a well defined number of equal 13L. Boltzmann, “On the relation between the second law of thermodynam- parts.” Recently, Darrigol summarized this controversy in an ics and the probability calculations of the principles of thermal equi- article titled, The Historians’ Disagreement over the librium,” Wien. Ber. 76, 373–435 (1877); Reprinted in Wissenschaftliche 7 Abhandlungen von Ludwig Boltzmann (Chelsea Publishing Company, Meaning of Planck’s Quantum. New York, 1968), Vol. 2, pp. 164–223. It appears that the disagreement among historians of sci- 14G. Holton and Stephen G. Brush, Introduction to Concepts and Theories in ence and physicists is based on a different understanding of Physical Science (Addison-Wesley, 1973). the relation between Boltzmann’s seminal 1877 article estab- 15A. Pais, Subtle is the Lord, The Science and the Life of Albert Einstein (Oxford Press, New York, 1982), pp. 370–371. lishing the relation between entropy and statistical physics, 16 and Planck’s application of this work to obtain a physical ba- R. Feynman, R. B. Leighton, and M. Sands, The Feynman Lectures in Physics (Addison-Wesley, 1963), Vol. 1, pp. 41–46. sis his black-body formula, which he had obtained previously 17Lord Rayleigh, “Remarks upon the law of complete radiation,” Philos. by an empiricalfit to experimental data based on classical Mag. XLIX, 539–540 (1900); “A comparison of two theories of radi- thermodynamics and electrodynamics. Unfortunately, many ation,” Nature 72, 293–294 (1905). of Planck’s documents and correspondence that could have 18In the limit of vanishing, Boltzmann’s discrete model is only applicable to the motion of molecules in two dimension (See Ref. 13, p. 190). illuminated the development and early reception of his ideas 19 were destroyed during the bombing of Berlin in 1944. In this M. Planck, “Zur theorie des gesetzes der energieverteilung im normal spectrum,” Verh. Dtsch. Phys. Ges.2, 237–245 (1900). connection, it is worthwhile to recall Einstein’s observation 20See Ref. 15 p. 372. that “If you want tofind out anything from the theoretical 21A. Einstein, “On a heuristic point of view concerning the production and physicists about the methods they use, I advise you to stick tranformation of light,” Ann. Phys. 17, 132–148 (1905). closely to one principle: do not listen to their words,fix your 22M. Planck, Scientific Autobiography, translated from German by F. Gaynor attention on their deeds.”46 (Philosophical Library, New York, 1949), pp. 39–41; “Wissenschaftliche selbstbiographie,” Acta Hist. Leopold. 19, 16–17 (1990). 23 1 M. Planck, “The genesis and present state of development of the quantum L. Rosenfeld, “La premiere phase de l’e`volution de la Theòrie de Quanta,” theory, Nobel lecture, June 2, 1920,” in Nobel Lectures, Physics Osiris 2, 149–196 (1936). 2 1901–1921 (Elsevier, Amsterdam, 1967), pp. 407–420. L. Rosenfeld, “Max Planck et la de`finition statistique de l’entropie” in 24C. Jungnickel and R. McCormmach, Intellectual Mastery of Nature: Max Planck Festschrift, edited by B. Kockel, W. Macke, and A. Theoretical Physics from Ohm to Einstein (University of Chicago Press, Papapetrou (Veb Deutscher Verlag Der Wissenschaften, Berlin, 1958), pp. Chicago, 1986), pp. 261–262. 203–211. 25A. Hermann, , originally published by 3 The Genesis of Quantum Theory M. Klein, “Max Planck and the beginnings of the quantum theory,” Arch. Physik Verlag, Mosbach/Baden, under the title Frugeschichte€ der Hist. Exact Sci. 1, 459–479 (1961); “Thermodynamics and quanta in Quantumtheorie (1899–1913), English translation by C. W. Nash Planck’s work,” Phys. Today 19(11), 23–32 (1966). (Massachusetts Institute of Technology, Cambridge, MS, 1971), pp. 23–24. 4 For an excellent historical article on Planck’s development of the quantum 26W. Wien, “Uber€ die Energievertheilung im Emissionsspectrum eines theory, containing also an extensive list of references, see C. A. Gearhart, schawrzen K€orpers,” Ann. Phys. 294, 662–669 (1896). “Planck, the quantum, and the historians,” Phys. Perspect. 4, 170–215 27L. Boltzmann, “Ableitung des stefanschen gesetzes, betreffend die abh€an- (2002); See also H. Kragh’s account in Quantum Generations (Princeton gigkeit der w€armestrahlung von der temperature aus der elektromagneti- U. P., Princeton, 1999), pp. 58, 63; and his article “Max Planck, the reluc- schen lichttheorie,” Ann. Phys. 22, 291–294 (1884). tant revolutionary,” Phys. World 13, 31–35 (2000); For biographies of 28M. Planck, “Ueber eine verbesserung der wien’schen spectralgleichunge,” Planck, see J. L. Heilbron, The Dilemmas of an Upright Man: Max Planck reprinted in Max Planck, Physikalische Abhandlungen und Vortrage€ as Spokesman for German Science (University of California Press, (Friedr. Wieweg & Sohn, Braunschweig, 1958), Vol. I, pp. 687–689. Berkeley, CA, 1986); B. R. Brown, Planck, Driven by Vision, Broken by 29M. Planck, “On irreversible radiation processes,” reprinted in Max Planck, War (Oxford U. P., New York, 2015). Physikalische Abhandlungen und Vortr€age (Friedr. Wieweg & Sohn, 5 T. Kuhn, Black-Body Theory and the Quantum Discontinuity, 1894–1912 Braunschweig, 1958), Vol. I, pp. 493–600. (Oxford U. P., New York, 1978); “Revisiting Planck,” Hist. Stud. Phys. 30A. Franklin, The Neglect of Experiments (Cambridge U. P., Cambridge, MS, Sci. 14(2), 231–252 (1984). 1986), p. 1. Franklin wrote that one of the greatest anticlimaxes in all of lit- 6 R. Jost, “Planck-Kritik des T. Kuhn,” in Das Marchen€ von Elfenbeinernen erature occurs at the end of Shakespeare’s Hamlet. On a stage strewn with Turm: Reden un Aufsatze€ , Lecture Notes in Physics Monographs, German noble and heroic corpses—Hamlet, Laertes, Claudius, and Gertrude—the Edition (Springer, 1995), pp. 67–78. In passing, Jost writes: “Im Lichte ambassadors from England arrive and announce that “Rosencrantz and dieser Feststellung aber bewundere ich Herrn Kuhns Ungehemmtheit, uns Guildenstern are dead.” No one cares. A similar reaction might be produced seinen Unsinn aufzutischen,” which roughly translates “what Kuhn has among a group of physicist, or even among historians and philosophers, been dishing us is nonsense.” were someone to announce that “Lummer and Pringstein are dead.” 7O. Darrigol, “The historians’ disagreement over the meaning of Planck’s 31Historians of science have followed Klein’s statement that “it seems most quantum,” Centaurus 43, 219–239 (2001); “The quantum enigma,” in The likely that Planck was guided by the form Wien’s distribution law,” when Cambridge Companion to Einstein, edited by M. Janssen and C. Lehner if fact there was not any other alternative. (Cambridge U.P., Cambridge, 2014), pp. 117–142. 32See Ref. 29, p. 597. 8S. G. Brush, Statistical Physics and the Atomic Theory of Matter 33O. Lummer and E. Pringsheim, “Die verteilung der energie in spectrum (Princeton U. P., Princeton, 1983); R. Balian, From Microphysics to des schwarzen k€orpers,” Verh. Dtsch. Phys. Ges.1, 23–41 (1899). Macrophysics, Methods and Applications of Statistical Physics (Springer 34H. Rubens and F. Kurlbaum, “Uber€ die emission langwelliger Verlag, Berlin, 1992), Vols. I and II. w€armestrahlen dur die schwarzen k€orper bei verschieden termperaturen,” 9D. M. Greenberg, N. Erez, M. O. Scully, A. A. Svidzinsky, and M. S. Preussiche Akad. Wiss. 929–941 (1900). Zubairy, “Planck, photon statistics, and Bose-Einstein condensation,” 35H. Rubens and E. F. N. Nichols, “Versusche mit w€armerstraheln von Prog. Opt. 50, 275–330 (2007). grosser wellenl€ange,” Ann. Phys. 60, 418–496 (1897). 10S. Seth, “Quantum physics,” in Handbook of the History of Physics, edited 36M. Planck, “Uber€ des gesetzes der energieverteilung in normal spectrum,” by J. Buchwald and R. Fox (Oxford U. P., New York, 2013). Ann. Phys. 309(3), 564–566 (1901).

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This article is copyrighted as indicated in the article. Reuse of AAPT content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 129.175.80.177 On: Fri, 30 Sep 2016 08:37:01 37 It should be pointed out that it was Planck’s very good fortune that and the ration j=n isfinite corresponding to the fraction of molecules Boltzmann’sfirst treatment of his molecular gas model was in two dimen- with energyj. sions. For each degree of freedom, the classical mean energy of a molecule 41J. C. Maxwell, “Illustrations of the dynamical theory of gases,” Philos. 1 3 isU 2 kT. Hence the physical three dimensional case withU 2 kT would Mag. 19, 19–32 (1860); ibid. 20, 21–37 (1860); reprinted in The Scientific not¼ have been a useful model for Planck’s electrical oscillators.¼ Papers of James Clerk Maxwell (Dover Publication, Inc, New York, 1965) 38But this constraint onp does not apply in the Stirling approximation for pp. 377–409. the factorials in WB. In his book (Ref. 5, p. 49), Kuhn setsp k and states 42See Ref. 13, p. 190. that “standard variational techniques lead directly to the conclusion¼ that 43M. Klein, “Contribution to paradigm lost, a review symposium,” ISIS 70, forp n,”n j is given by Boltzmann’s classical expression, Eq. (A18). 429–433 (1979). But this claim is incorrect, because to obtain the distribution in the classi- 44P. Galison, “Kuhn and the quantum controversy,” Br. J. Philos. Sci. 32, cal limit, Boltzmann setp andk n. 71–85 (1981). 39Boltzmann also considered¼1pfinite, but the case of interest related to 45A. A. Needell, “Review of “Black-Body Theory and the Quantum Planck’s formula corresponds top . Discontinuity,” by Thomas Kuhn,” ISIS 78, 604–605 (1987). 40 !1 46 In the Stirling approximation the resulting values ofn j, Eq. (A7), are not A. Einstein, Ideas and Opinions (Crown Publishers, New York, 1954), p. integers. In this casek andn are also infinite, but the ratiok=n isfixed 270.

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