The years of the third decade of the present century were heady times. Old social orders were being swept away, monarchies becoming republics and the United States of America was emerging as a world power. In physics too, revolutions were taking place, none more potent than that which resulted in the emergence of quantum mechanics as a model for the behaviour of sub-atomic particles. It was Newton who first suggested that light was particulate but during the nineteenth century this view had fallen into neglect. Indeed a number of experiments, for example the classic Young's slits experiment, demonstrated quite conclusively that light was a wave motion. How else could interference fringes occur? However, the experiments on the photoelectric effect demonstrated just as conclusively that light energy was carried in packets, or quanta, and that a continuous wave description was not applicable. This ‘wave or particle’ dilemma was not unique to the behaviour of light. J. J. Thompson showed that cathode rays were charged, had a well defined mass and had all the properties expected of a beam of particles. Nevertheless, Davisson and Germer showed that diffraction of electrons could take place, an effect made visually much more dramatic by G. P. Thompson's transmission electron diffraction patterns. Nowadays, electron diffraction is used as a routine analytical tool in all advanced metallurgical and materials science laboratories (Fig. 2.1). Clearly new axioms were required.
The years of the third decade of the present century were heady times. Old social orders were being swept away, monarchies becoming republics and the United States of America was emerging as a world power. In physics too, revolutions were taking place, none more potent than that which resulted in the emergence of quantum mechanics as a model for the behaviour of sub-atomic particles. It was Newton who first suggested that light was particulate but during the nineteenth century this view had fallen into neglect. Indeed a number of experiments, for example the classic Young's slits experiment, demonstrated quite conclusively that light was a wave motion. How else could interference fringes occur? However, the experiments on the photoelectric effect demonstrated just as conclusively that light energy was carried in packets, or quanta, and that a continuous wave description was not applicable. This ‘wave or particle’ dilemma was not unique to the behaviour of light. J. J. Thompson showed that cathode rays were charged, had a well defined mass and had all the properties expected of a beam of particles. Nevertheless, Davisson and Germer showed that diffraction of electrons could take place, an effect made visually much more dramatic by G. P. Thompson's transmission electron diffraction patterns. Nowadays, electron diffraction is used as a routine analytical tool in all advanced metallurgical and materials science laboratories (Fig. 2.1). Clearly new axioms were required.
[M]odern physics has definitely decided in favor of Plato. In fact the smallest units of matter are not physical objects in the ordinary sense; they are forms, ideas which can be expressed unambiguously only in mathematical language. Werner Heisenberg Basic framework Prerequisites: Appendix C, §1B(ii). Near the beginning of the twentieth century, physicists realized that electromagnetic waves sometimes exhibited particle-like properties, as if light were composed of discrete ‘photons’. In 1923, Louis de Broglie proposed that, conversely, particles of matter might have wave-like properties. This was confirmed in 1927 by C. J. Davisson and L. H. Germer and, independently, by G. P. Thompson, who showed that an electron beam exhibited an unmistakable diffraction pattern when scattered off a metal plate, as if the beam were composed of ‘electron waves’. Systems with many interacting particles exhibit even more curious phenomena. Quantum mechanics is a theory which explains these phenomena. We will not attempt here to provide a physical justification for quantum mechanics. Historically, quantum theory developed through a combination of vaguely implausible physical analogies and wild guesses motivated by inexplicable empirical phenomena. By now, these analogies and guesses have been overwhelmingly vindicated by experimental evidence. The best justification for quantum mechanics is that it ‘works’, by which we mean that its theoretical predictions match all available empirical data with astonishing accuracy.
We tried to introduce the idea of quantization in Chapter 9 as a completion of a one semester course. However, we skipped over some really interesting events in the history of Science between 1900 and 1913 when Bohr derived the quantized energy of the H atom. First we want to carry out the 1901 Planck derivation of the formula for blackbody radiation [1]. Many texts just show the curve, write e¼ hn, and move on. As a student, this author found that limited explanation very frustrating since energy quantization is a fundamental concept. Even among graduate texts in quantum mechanics, we are aware of only one that does the complete treatment which we will draw upon for the mathematics [2] but supplement with a narrative that we have found helpful to students over the years. Then in 1905, Albert Einstein (1879-1955), one of the most influential scientists of all time, gave an explanation of the photoelectric effect [3] for which he received the Nobel Prize in 1921. Even reducing our list to essential topics, we need to discuss the Davisson-Germer experiment [4]. The photoelectric effect introduces the idea that light waves can act as particles while the Davisson-Germer experiment showed that particles can act like waves and confirmed the De Broglie equation [5]. However, you can be assured that it will not be as difficult as you might have anticipated and if you can absorb the meaning of just these three key experiments you should be able to begin thinking in terms of quantum mechanics! Despite our slow historical development, this is 2010 and we have to get to the twenty-first century somehow!
Toward the end of the nineteenth century, it became clear that some experiments cannot be explained on the basis of known physics, now referred to as classical physics. In 1900, Max Planck was able to correctly describe the distribution of blackbody radiation energy as a function of wavelength λ or frequency ν = c/λ. He had to accept the existence of energy packets (quanta) with energy E = hν. A few years later, Albert Einstein found that this unexpected relation between energy and frequency is also necessary in order to understand photoemission from metallic surfaces. A decade later, Niels Bohr arrived at the correct equation for the electronic spectrum of the hydrogen atom by applying “quantum conditions” on the motion of the electron around the nucleus and the Planck’s relation E = hν on the energy difference between the energy levels (1916). A decade later, Heisenberg, Born, and Jordan introduced “quantum mechanics” and de Broglie and Schrödinger (1925-1926) introduced “wave mechanics.”
By the end of the nineteenth century all the important elements of classical physics were fully mature. Newton's Laws had been applied with success to everything from industrial machines to planetary orbits. Classical thermodynamics had extended energy conservation arguments into thermal processes, and scientists including J. Willard Gibbs and Ludwig Boltzmann had developed the statistical interpretation of entropy. James Clerk Maxwell had explained all electromagnetic phenomena, from AC generators/motors to light, with the four Maxwell's equations and three material-dependent constitutive relations. There was serious discussion that physics was on the verge of being “finished” – becoming a closed system of knowledge like classical geometry with only essentially routine tasks left of determining how the known laws could be applied to engineering problems. Yet by 1930 the foundations of mechanics, electromagnetics, and atomic-scale systems had been shaken to the core by the new revolutions in the Theory of Relativity, the photon picture of light, and quantum physics. We are still reaping the benefits of the application of these new scientific paradigms in our technology today, including semiconductor electronic devices, lasers, and GPS systems. But the description of reality that these theories provide is still deeply anti-intuitive and disturbing. Nevertheless, quantum physics is one of the most extensively experimentally verified theories that we know. Even when quantum theory and common sense seem to diverge, quantum theory gives the right answers when tested by experiment. In the next chapter we will develop the framework of quantum theory that has been so successful when people “shut up and calculate,” as one scientist suggested as the way through the philosophical thicket of quantum physics. But in this chapter, we will spend a brief time considering the historical development and continuing paradoxical implications of quantum theory. The photoelectric effect and photons In 1905, Albert Einstein, who was a key figure in the revolution of modern physics, was working as a clerk in the patent office in Zurich, Switzerland. Einstein had finished his studies in physics, but had not obtained a coveted position as a university professor. He was intensely interested in the latest developments in classical physics and was aware of a few of the remaining loose ends that were resisting explanation in the classical model.
In the early 1900s more and more experimental evidence was accumulated indicating that microscopic particles show wave-like properties in certain situations. These particle-wave features are very evident, e.g., in measurements where electrons are diffracted from a double slit to propagate toward a screen where they are detected. Based on the classical averaging of particles discussed in Section 1.2.2, one expects that the double slit only modulates the overall intensity, not the spatial distribution. Experimentally, however, one observes a nearly perfect interference pattern at the screen implying that the electrons exhibit wave averaging features such as discussed in Section 2.1.2. This behavior, originally unexpected for particle beams, persists even if the experiment is repeated such that only one electron at a time passes the double slit before it propagates to the detection screen. Thus, the wave aspect must be an inherent property of individual electrons and not an ensemble effect. Another, independent argument for the failure of classical physics is that the electromagnetic analysis of atoms leads to the conclusion that the negatively charged electron(s) should collapse into the positively charged ion because the electron–ion system loses its energy due to the emission of radiation. As we will see, this problem can be solved by including the wave aspects of particles into the analysis. In particular, as discussed in Section 2.3.3, waves can never be localized to a point without increasing their momentum and energy beyond bounds.
The evolution of light theories began with Isaac Newton's corpuscular model, which explained reflection and refraction but could not account for diffraction and interference. In contrast, Christiaan Huygens proposed a wave theory, explaining light's behavior through an ether-based medium, supported by his principle that each point in a wavefront acts as a secondary source. This idea was experimentally supported in the early nineteenth century when Thomas Young's double-slit experiment revealed an interference pattern, affirming light's wave nature. Later, James Clerk Maxwell unified electricity and magnetism, establishing light as an electromagnetic wave and extending the electromagnetic spectrum beyond visible light. In the twentieth century, Einstein's photoelectric effect introduced the concept of wave-particle duality, demonstrating that light behaves as discrete photons. Soon after, Louis de Broglie extended the idea of wave-particle duality to matter, a prediction confirmed in 1927 when Clinton Davisson and Lester Germer observed electron diffraction from a crystal and, independently, G.P. Thomson demonstrated electron diffraction through thin films, both proving that electrons also exhibit wave-like properties. This concept was dramatically visualized by Claus Jonsson's 1961 electron double-slit experiment. Recently, the ALICE collaboration observed quantum interference patterns at the femtometer scale in ultra-relativistic nuclear collisions, pushing quantum interference studies to new frontiers.