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Breif Introduction to Quantum Mechanical History By Cisco Jimenez

Max Planck did not at first subscribe to the belief that atoms and molecules were real entities1. He was in fact a reserved scientist who avoided what he termed all doubtful adventures. However, his work on black body radiation lead to his eventual conversion to the atomist doctrine. One of the most heated conflicts between the two opposing schools of thought at the time was the interpretation of the second law of thermodynamics. The debate initially manifested itself through an argument between Ludwig Boltzmann and Plancks assistant, Ernst Zemelo, who attempted to show that Boltzmanns interpretation contradicted itself. Boltzmann pointed out that the second law was often misinterpreted, and that the true deciding factor was that of statistics. Statistically speaking, it is only much more likely to find a system favoring a higher state of entropy, and that while not probable, is it still possible to observe an event in direct contradiction to the second law of thermodynamics. This interpretation of the second law of thermo really bothered Planck, and he set out to refute Boltzmann using the physics involved with black body radiation2. Much work had already been done at that time on black body radiation, including that by Gustav Kirchhoff, who found that the ratio of radiation emitted from an experimental radiator to that absorbed by the same radiator had nothing to do with size, shape, nor material, but instead seemed to imply some sort of fundamental property of the radiation itself. In addition, Willhelm Wein devised his displacement law in 1896, establishing a mathematical 1 Referred to then as the atomist doctrine 2 At the time, referred to as cavity radiation

relationship between radiation frequency and experimental cavity temperature. Weins displacement law was supported by experimental data gathered by Freidrich Paschen, but was later shown to fall apart at lower frequencies of radiation in experiments carried out by Otto Lummer and Ernst Pringsheim. This all set the stage for a visit to Planck by physicist Heinrich Rubens, who shared with Planck some of his latest experimental data. The results he was shown inspired Planck and he set to work. Using Weins law, he was able to adapt it to fit a function that described the behavior of these radiators perfectly, at any frequency of radiation. By the time he was done, his equation had two fundamental constants, relating to radiation frequency and to temperature. The constant relating to radiation frequency, or h, eventually became known as Plancks constant, and it remains one of the most important constants used in quantum mechanics. However, even though Planck was able to find a radiation law that described all available data, he did not have a theoretical basis for the law. Planck had been initially looking at the problem in terms of oscillators being acted upon by an electromagnetic field. Planck believed that the oscillators would behave in way that would enable the energy of the system to be distributed evenly throughout the system, which had allowed him to derive an expression for a single oscillator in a given cavity wall, acted upon by a given EM field. However, his equation had been found by matching experimental data, and he needed to drive a similar expression from scratch for any meaningful understanding of the source of the mathematics and physics. Unfortunately for Planck, in order to achieve this, he found himself drifting mathematically toward the statistical models of his main rival, Boltzmann.

Boltzmann had been looking at an entirely different problem, but his statistical approach had led him to a form of energy quantization he referred to as buckets. Boltzmanns buckets, while subtly different, were eventually the inspiration for Planks probability distributions for black body radiators. Eventually, in a wonderful twist of irony, by applying statistical methods similar to those used by his rival Boltzmann, Planck was able to derive his now famous equation: =h, where was required to be discrete integer multiples of h. Planck presented these findings on December 14th, 1900, a year now widely acknowledged as the birthday of the quantum revolution. However, even Planck did not fully understand the full impact of what he had done. He still thought of energy as a continuous and uninterrupted flow. It would be another who was to eventually help understand the full physical significance of what Planck had done. In the year 1905, Albert Einstein is said to have had his annus mirabilis, or miracle year. At the age of 26, he wrote five different papers, which eventually rocked the very foundations of classical physics. The first of these papers, written in March 1905, addressed the problems that arose as the result of Plancks mathematical trick, in which Planck had used a mixture of quantum and classical mechanics to derive his radiation law. This was a problem, because the purely classical derivations all produced laws that failed.3 Einstein finally realized that the reason Plancks law worked for all the data was because he had mixed in statistical methods with classical physics. In essence, he saw that purely classical explanations failed to adequately explain certain phenomena. Classical methods treated

3 Weins Radiation law fit the experimental data well at high frequencies but failed at lower frequencies, while the Raleigh-Jeans law fit well at high frequencies and failed at low frequencies.

energy as a continuous function, and Planck had changed this inadvertently when he had introduced statistics to his methods. Einstein saw that this was very important. Strong evidence existed at the time supporting the particulate nature of matter, and the wave-like nature of radiation. Einstein also believed that light could possess particulate properties similar to those of matter, and in an idea he dubbed the heuristic principle, he described for the first time his incredible idea of wave-particle duality. This would be the first time in over 200 years that light would be thought of in this manner, it was a return to the corpuscular theory of light introduced by Isaac Newton. Einstein postulated that light could only be emitted and absorbed as discrete energy packets. However, unlike Newton, he was not abandoning the wave-like nature of light. Rather he was insisting that the two properties of light being experimentally observed were simply different versions of the same thing: wave phenomena were simply the time-averaged, collective motions of many light-quanta rather than the instantaneous snapshot of an individual light quanta. This was an incredibly radical idea at the time, and was not readily accepted by Einsteins peers, but was something that was demonstrated elegantly by the experimental data observed in the photoelectric effect. The photoelectric effect was a phenomenon that had been unexplainable for some time, but was solved by Einstein by applying his ideas on light quantization. Experimental data had shown that shining light on metal surfaces caused electrons to be ejected from the metal. However, contrary to what was expected based on the wave model of light, the energy of ejected electrons did not increase with an increase in intensity of light. Rather, it increased with an increase in light frequency. Einstein correctly assumed that this was due to the quantized packets of energy in light. Increasing intensity did not increase the size of

the photons, but rather increased their abundance, which resulted in more ejected electrons, but electrons ejected at the essentially the same energy level. Einstein took this a step further, relating Plancks equation to electromagnetic radiation in a way that made it universally relevant to light in any situation, not just appropriate to black body radiation, as Planck had believed. The next main player in our quantum story was Danish physicist Niels Bohr. English physicist Joseph John Thompson had shown experimentally the existence of electrons in 1897, implying that atoms could no longer be thought of as indivisible particles. Further work by Ernest Rutherford in 1909-1911 showed the existence of something else within the atom4, which led Rutherford to postulate that atoms were mostly empty space, with electrons moving about, similar to planets orbiting our sun. The core of Rutherfords idea has remained mostly unchanged, even to this day. In the movie Mindwalk5, the trio discussed this idea in detail, giving many analogies to help viewers comprehend the reality of things vibrating, rotating and translating all around us and even within us. The planetary model remains a compelling way to help visualize the atomic scale, because if one makes a direct comparison between an atom viewed in this simplified manner and our solar system, the outer electron of a hydrogen atom would be where Pluto is (5.9 billion km), and the nucleus would be a tenth the size of our sun (69,550 km). That means the outer electron would be about 84,892 nuclear diameters away from the nucleus. Of course, in 1909, when Rutherford was performing his experiments, very little of this was fully known or understood. In fact, the main competitor to Rutherford at the time 4 Unknown by Rutherford at the time, he had experimentally shown the existence of the atomic nucleus. 5 1990, Starring: Liv Ullmann, Sam Waterson, John Heard. Directed by: Bernt Amadeus Capra.

was Thompson. Thompsons model involved stationary electrons embedded in positively charged medium, like raisins in plum pudding. Indeed, this is what Thompson is most widely remembered for today: his Plum Pudding model of the atom. The main reason Thompson, Rutherford, and rest of the general physics community were reluctant to initially accept the idea of electronic motion within the atom, was the problem of charged particles moving about in an electromagnetic field. The very motion of the electrons, according to classical physics, would cause them to lose energy, and become less and less likely to resist the pull of the nucleus. By the laws of classical physics, atoms with moving electrons would collapse in on themselves, effectively ending all existence. Niels Bohr had initially been working for Thompson, but became quickly frustrated, as the two did not appear to have gotten along so well. In 1911, Bohr went to work for Rutherford, with the approval of Thompson. Bohr eventually began to use the ideas of Einstein and Planck in his approach to the problem of classical physics failure to explain the atomic model. Classical mechanics was failing, so Bohr pulled an Einsteinthe current laws were incapable of dealing with his problem, so he made his own rules by working backwards from his assumption. Bohr assumed that the orbits in atoms would be ordered in a fashion connected to the ordering of energy in Plancks cavity oscillators, so he began with this assumption. Orbitals would be specifically ordered in integer multiples of h. It was slow going, with many problems plaguing Bohrs model, but in 1913 Hans Hansen, a colleague of Bohrs, shared with him data from Balmer and Rydberg that provided the final piece of the puzzle Bohr would need. In 1885, Johann Jakob Balmer, a Swiss mathematician, had found a formula for a simple mathematical pattern he noticed in hydrogen emission

lines. Swedish physicist Jonhannes Rydberg had generalized the formula in 1888, but neither Balmer nor Rydberg had seen the meaning behind their data fitting. However, to Bohr, this hydrogen emission pattern presented exactly the evidence for which he had been searching. Bohr believed the mathematical patterns in the hydrogen spectra lines were the direct result of the discrete ordering of atomic orbitals. In fact, it tied directly in with Plancks ideas, as he had believed. Any time an electron jumped from one orbital to another, lower orbital, it released a corresponding fixed amount of radiation, which generated the precise spectra documented by so many. This fit so well with Bohrs ideas, that he was able to derive results in full agreement with the Balmer and Paschen series purely theoretically, as well as predict several as yet unseen emission series in the UV and IR regions of the EM spectrum. In addition, Bohr was also able to calculate and demonstrate the source of the Rydberg constant using only fundamental physical constants, including Plancks constant, and was also able to explain data obtained by Edward Charles Pickering, which involved half-integer numbers not allowed in Bohrs theory. Bohr re-wrote the numbers as whole integers and showed that they were from spectra generated by ionized helium rather than hydrogen. A noteworthy consequence of Bohrs theory was that along with fixed and stable electron orbitals came fixed angular momentum, which was found to be h/2. Despite the apparent success of Bohrs theory, there were still some problems and unexplained phenomena. How did the transition from one orbit to another happen? It could only be possible if done instantaneously. If the transition were made slowly, a tremendous amount of energy would be involved, as the result of the classical mechanics describe above. In addition, if this transition were to be assumed to be instantaneous, how would

the electron making the jump emit the exactly correct amount of radiation to end up in the correct destination orbital? Just where did the quantum numbers come from? The next big piece of the quantum puzzle was to be found by Prince Louis DeBroglie, of France. Bohr had shown that electrons do indeed move about within an atom, and that they do so only in specific, stable orbits, with fixed angular momentum. However, it would be DeBroglie, in 1923, who would use ideas from Einsteins theories to make the next quantum leap, and show from whence the quantum numbers originate. DeBroglie decided that Einsteins theories of relativity and light-quantum could be and should be extended to apply to all matter, especially electrons. This was really the first time an electron, a form of matter, had been thought of as both a wave and a particle. DeBroglie wrote: That which makes an electron an atom6 of energy is not its small volume that it occupies in space, I repeat: it occupies all space, but the fact that it is undividable, that it constitutes a unit. This was an incredible thought in and of itself, but DeBroglie was far from done. He connected the equation relating energy and frequency (=h) with the equation relating energy and mass (=mc2), and reduced this to his now famous relationship: =h/p, where p represents the momentum of a particle. DeBroglie postulated that only the extremely small size of Plancks constant is what limits what he described as matter waves or phase waves from being visible in larger, more classical systems. This was an idea that I believe is tied into Bohrs correspondence principle. I believe that the switching point between classical and quantum mechanics revolves somehow around Plancks constant. I say this only because it rears itself every time a bridging between classical and quantum theory is made. Either way, DeBroglie also said that these 6 In this case, I believe DeBroglie was using the word atom with respect to its original Greek meaning: atomos (), or indivisible.

matter waves could not be similar to classical waves in terms of energy and velocity, for if such were the case, they would exceed the speed of light. DeBroglie believed them to be representative of a matter distribution in space, and it was his love of music that eventually helped him to make his next major breakthrough. Musical notes and pitches are explained by classical physics as originating from standing waves. These are sinusoidal patterns produced by vibrations of a fixed length of string or a fixed size resonator, like a human voice box. The key is that the waves are only free to vibrate on a pre-defined region, and the ends of the waves are tied down and must always be zero. Here is where DeBroglie used music as the inspiration for something incredible: the quantum numbers from Bohrs atomic model were mathematically inherent if the electrons were treated as standing waves confined to specific circular orbits. If his idea were true, it would require electron matter waves to have harmonic resonance that fit precisely within the circumference of a given orbit. The electron matter wave could only exist if the beginning and ending amplitudes for one circular orbit were identical: it had to end exactly where it started7, or it would cancel itself out destructively. DeBroglie described this as the resonance condition, and it beautifully explained the stability of Bohrs quantum numbered electron orbitals. While this idea was incredible, it was also very radical, and most of the scientific community at the time was unwilling to accept it. DeBroglie had made a theoretical connection, but had not been able to mathematically derive any proof of his ideas. In addition, DeBroglies idea still did not explain the causality or the nature of quantum jumps. What DeBroglie did say was that the current quantum mechanical model was no longer sufficient to explain the inner workings of the atom. Something new was needed. Einstein, 7 This is similar to the ends of a standing wave being tied down at both ends.

who was also becoming increasingly concerned with the inability of quantum theory to explain an ever-increasing amount of experimental data, shared DeBroglies feelings. There were those in the scientific community who felt the opposite however, and continued to try and use a hybrid classical-quantum theory, despite its increasing failure. Most notably of these was Niels Bohr, who along with Hendrik Kramers and John C. Slater proposed a theory in direct opposition to Einsteins light-quantum theory. The BKS8 theory, proposed in early 1924 sought to replace Einsteins light-quantum theory with one involving statistical averaging. The theory proved disastrous however, and was disproved my experimental data by 1925. Classical-quantum hybrid theory was just not adequate, and in that same year, it was Werner Heisenberg who would realize this most clearly, and attempt to build a new set of rules from the ground up. Heisenberg realized that a hybrid classical-quantum mechanical model was

insufficient to explain the internal workings of atoms, and he decided that in order to make any progress, it must be discarded completely. Heisenbergs first decision was to avoid using anything that was not directly observable. This left him with few choices, and he chose to work with the intensities and frequencies of line emission spectra, the observable properties originating from quantum jumps between atomic orbitals. Using Fourier infinite series, he constructed an elaborate table of harmonic matter waves with each term of the series having an amplitude and a frequency that corresponded to one of the quantum jumps of an electron between orbitals. Heisenberg became excited because when he had finished, his calculations for energy were all working for different orbits, and were in agreement with conservation of energy laws. There was one problem with his calculations, 8 This is short for Bohr-Kramers-Slater

however: he was only able to calculate one physical property at a time for certain situations, meaning at times xy yx. This troubled him, but he shared his work with Max Born, whom he had been working with previously in Gttingen. Born recognized what Heisenberg had unknowingly done: he had been using a rule for multiplication of matrices, which explained the odd situations in which properties did not commute. Born took Heisenbergs work and began to work on it in earnest with his student,

Pascual Jordan. They began to apply rules of matrix multiplication and had some very interesting results. Energy matrices were all diagonalized, and further the matrix calculations for position and momentum did not commute.9 Heisenberg, Born, and Jordan published a paper on their findings in November 1925. The paper eventually found its way into the hands of PAM Dirac, who saw the implications of these new matrix mechanics. Using this new approach, Dirac was able to independently calculate the position- momentum factor9, prove that energy conservation was upheld, and derived from pure theory the quantum numbers corresponding to stable atomic orbitals that Bohr had gotten from experimental data but never derived. This was an incredible accomplishment. Even though this new theory of matrix mechanics was in its infancy, it showed great promise. Of course as with every other radical new idea, most of the scientific community remained unimpressed. 9 The difference between the momentum matrix p, and the position matrix q was found to be equal to ih/2.

 Authors Note: 3,623 Words 62 Adverbs 0.0171 [adverb:word] Ideally it should be somewhere around h.