The early twentieth century was a revolutionary time in the history of physics. People often think of Einstein's special theory of relativity of 1905, which changed our conceptions of time and space. But among physicists, quantum mechanics is usually regarded as an even more radical change in our thinking about the physical world. Quantum mechanics, which was developed between 1900 and 1926, began as a theory of atoms and light but has now become the framework in terms of which all basic physical theories are expected to be cast. We need quantum ideas not only to understand atoms, molecules, and elementary particles, but also to understand the electronic properties of solids and even certain astronomical phenomena such as the stability of white dwarf stars. The theory was radical in part because it introduced probabilistic behavior as a fundamental aspect of the world, but even more because it seems to allow mutually exclusive situations to exist simultaneously in a “quantum superposition.” We will see later that the possibility of quantum superposition is largely responsible for a quantum computer's distinctive advantage over an ordinary computer. The present chapter is devoted to introducing the basic principles of quantum mechanics. There are essentially four components of the mathematical structure of quantum mechanics. We need to know how to represent (i) states, (ii) measurements, (iii) reversible transformations, and (iv) composite systems. We will develop the first three in stages, starting with a very simple case – linear polarization of photons – and working toward the most general case.
The early twentieth century was a revolutionary time in the history of physics. People often think of Einstein's special theory of relativity of 1905, which changed our conceptions of time and space. But among physicists, quantum mechanics is usually regarded as an even more radical change in our thinking about the physical world. Quantum mechanics, which was developed between 1900 and 1926, began as a theory of atoms and light but has now become the framework in terms of which all basic physical theories are expected to be cast. We need quantum ideas not only to understand atoms, molecules, and elementary particles, but also to understand the electronic properties of solids and even certain astronomical phenomena such as the stability of white dwarf stars. The theory was radical in part because it introduced probabilistic behavior as a fundamental aspect of the world, but even more because it seems to allow mutually exclusive situations to exist simultaneously in a “quantum superposition.” We will see later that the possibility of quantum superposition is largely responsible for a quantum computer's distinctive advantage over an ordinary computer. The present chapter is devoted to introducing the basic principles of quantum mechanics. There are essentially four components of the mathematical structure of quantum mechanics. We need to know how to represent (i) states, (ii) measurements, (iii) reversible transformations, and (iv) composite systems. We will develop the first three in stages, starting with a very simple case – linear polarization of photons – and working toward the most general case.
Unlike special relativity, quantum mechanics was not the inspired product of one mind. It developed, in fits and starts, over a period of 25 years (1900–1925), and many cooks stirred the broth. Even now, a century later, quantum mechanics raises profound conceptual questions. Every competent physicist can “do” quantum mechanics, and the predictions it makes are in spectacularly good agreement with experimental results; there can be little doubt that quantum mechanics is “right.” On the other hand, as Richard Feynman once remarked, “nobody understands quantum mechanics.” I'll tell the story in two parts. First the history (how the essential pieces of the puzzle were assembled), and then the implications (what the finished picture has to say about our world). Photons Like relativity, quantum mechanics began with the study of light. In both cases, this historical association is misleading. Relativity, really, has nothing to do with light – to be sure, it involves that magic speed limit, c , and of course the most familiar thing that travels at speed c is light. So light is a convenient vehicle for introducing the subject. But it is perfectly possible to imagine a universe in which there is no such thing as light, and yet relativity might still be valid. Quantum mechanics, too, starts with light – in this case the “quantum” of light (the photon). But, as it turns out, this is just one rather specialized example of much more general principles – in fact, a rather bad example, because photons are by their nature relativistic (they travel at the speed of light), and it would be more natural to begin with the quantum mechanics of slow-moving objects, in analogy with Newtonian mechanics.
Quantum mechanics is a theory to explain and predict the behavior of particles such as electrons, protons, neutrons, atomic nuclei, atoms, and molecules, as well as the photon–the particle associated with electromagnetic radiation or light. From quantum theory we obtain the laws of chemistry as well as explanations for the properties of materials, such as crystals, semiconductors, superconductors, and superfluids. Applications of quantum behavior give us transistors, computer chips, lasers, and masers. The relatively new field of molecular biology, which leads to our better understanding of biological structures and life processes, derives from quantum considerations. Thus, quantum behavior encompasses a large fraction of modern science and technology. Quantum theory was developed during the first half of the twentieth century through the efforts of many scientists. In 1926, E. Schrödinger interjected wave mechanics into the array of ideas, equations, explanations, and theories that were prevalent at the time to explain the growing accumulation of observations of quantum phenomena. His theory introduced the wave function and the differential wave equation that it obeys. Schrödinger's wave mechanics is now the backbone of our current conceptional understanding and our mathematical procedures for the study of quantum phenomena. Our presentation of the basic principles of quantum mechanics is contained in the first three chapters. Chapter 1 begins with a treatment of plane waves and wave packets, which serves as background material for the subsequent discussion of the wave function for a free particle.
The difficulties of the old quantum theory were largely dispelled by the development of quantum mechanics in the 1920s. First Heisenberg (1925) developed the rather abstract matrix mechanics and soon after Schro¨dinger (1926; see also Eckart, 1926) developed the physically more appealing wave mechanics. Subsequently he showed them to be mathematically equivalent. The physicists were greatly relieved; now they had once again a mathematical formalism that enabled the results of experiments to be calculated. It was possible to move forward. It is certainly a very elegant and indeed beautiful formalism, and does enable the results of many physical measurements to be calculated with great accuracy. It is used daily by atomic and nuclear physicists; there is no other way to make calculations. From the earliest days there has been intense debate about the interpretation of quantum mechanics, and it shows no signs of being settled; if anything it is becoming more intense over the years. As Penrose has remarked, no one understands quantum mechanics. Feynman (1967; see also Sykes, 1994) also admitted that ‘nobody understands quantum mechanics’, and Einstein once remarked: ‘I have thought a hundred times as much about the quantum problems as I have about general relativity theory’ (Pais, 1994, p. 57). It should therefore be evident that the most that can be done here is to try to show where the real difficulties lie, and how the failure to recognize that quantum mechanics is an essentially statistical theory has led to a series of confusing quantum paradoxes. It is just these paradoxes that have often been used to support theological speculations. It is useful to ask what ‘understanding quantum mechanics’ actually means. Certainly it means being able to calculate the results of many measurements. The same applies to Newton’s theory of gravitation, which we understand in the sense that we can use it as a basis of calculation, although we do not really understand the gravitational force itself. Very often, especially in modern physics, the mathematical formalism does not give us the sort of intuitive physical feeling for what is going on that we often obtain from classical mechanics. Perhaps we can never achieve more than this for quantum mechanics. In classical mechanics we can assume that a property that is measured objectively exists prior to the interaction of the measuring apparatus with the observed system. Quantum mechanics, however, ‘is incompatible with the proposition that measurement discovers some unknown but pre-existing property’ (Peres, 1997, p. 14). There is an important distinction between mysteries and absurdities. We may be forced to live with mysteries, but there is no reason why we should put up with absurdities such as the wave-particle duality, tunnelling through potential barriers, acausal events and the collapse of the wave function. These are the quantum paradoxes that will be discussed later on. They arise within the Copenhagen interpretation of quantum mechanics and are solved by other interpretations. These alternative interpretations enable us to make conjectures about what is going on, even though we cannot understand it in detail. This is acceptable and a stimulus to further research. It is certainly difficult enough to understand quantum mechanics, but there is no need to try to visualize logical absurdities in the effort to do so. Quantum mechanics is a mathematical formalism that makes it possible to calculate the results of some experiments. Anything more than this, such as questions about the interpretation of what is measured and whether it tells us what is actually going on in the system being studied, belongs to philosophy. Thus we are concerned here with what is essentially a philosophical debate; if it were just a matter of physics the debate would have been settled long ago. One of the difficulties is that it invokes the results of experiments and uses the language of quantum mechanics. Inevitably this language uses philosophical terms and then it is easy to give the impression that the philosophical propositions are in some way entailed by the physical results. These in turn can influence theological thinking. In order to be quite clear which arguments are justified and which are not, it is essential to separate the three levels of discourse: physical, philosophical and theological. Our task is to relate these together, and this immediately raises the traditional problems of the philosophy of science, including the relation of experiment to theory, and of theory to explanation. We begin by discussing experiments, distinguishing between those that are real and those that are imaginary.
[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.
I conclude the first part of this book by carrying the story up to 1928, to the lightning flash in Eddington's mind produced by Dirac's paper on the wave equation of the electron. Setting out the context and Eddington's thinking about it is a very different matter for quantum mechanics and relativity. Both theories are commonly expressed in austere mathematical language. In the case of relativity the basic ideas behind the mathematics are now well understood and can be set out with little complication. These ideas were mostly already clear to Eddington. But for quantum mechanics the mathematics, yoked to the wealth of experimental results, drove the development of the theory at a breakneck speed, mostly without anyone pausing for deeper understanding. It is indeed only in the last decade that it has become generally accepted that quantum mechanics still lacks any coherent interpretation. To explain Eddington's context it is therefore necessary to say something about the mathematical formalism. It is true, as will become clear, that Eddington was a little more sceptical than most, but by and large the mathematics drove him as it did those directly working in the theory. I begin, then, with a description of that part of the early (pre-1925) history of quantum mechanics that was in Eddington's mind in 1923. Then I explain what happened in 1925–6 and Eddington's reaction to it. The chapter concludes with Dirac's relativistic wave equation of 1928 and Eddington's further reaction to that. The old quantum theory What is now called the old quantum theory arose at the turn of the century. Two related experimental contradictions with classical physics played important roles in this.
Chapter 4 deals with Quantum Mechanical (QM) phenomena. The first section describes the first attempts at quantization of energy, momentum, angular momentum, etc. We start with Plank's solution to the black-body problem, introducing the concept of photons: discrete packets of electromagnetic energy. We show how Plank's description of black-body radiation is perfectly fit by the cosmic microwave radiation, providing the strongest evidence for the Big-Bang at the origin of the Universe. We then describe Bohr's solution to the paradoxical stability of atoms, introducing quantization of angular momentum (or action) and correctly predicting the energy levels of the hydrogen atom. We show how Einstein used Plank's idea to explain the photo-electric effect (an effect exploited in CCD cameras and solar cells) and how he used Bohr's understanding of energy levels in atoms to provide an intuitive explanation of Plank's law. Einstein insight opened the way to the field of spectroscopy and the development of the laser. In the second section, following the lead of Dirac, we show that QM is equivalent to Linear Algebra in the space of complex functions (which describe the state of the system). We show that Schrödinger's equation is a natural consequence of that description, once the relation between energy and frequency established by Plank (for photons) and de Broglie (for particles) is taken into account. In the context of the chiral ammonia molecule we discuss the queerness of QM which describes physical systems as superposition of states (such as left and right chirality state of a molecule, dead and alive cat). We show that this queerness is nonetheless supported by experiments and is behind much of our technology: masers and lasers, atomic clocks, semiconductors (diodes, transistors, etc.). In the following section we introduce the representation of operators in QM (the equivalent of matrices in linear algebra): momentum, position, energy, etc. which correspond to measurements on the system. We show that the non-commutability of some operators (common with matrix operations) leads to Heisenberg uncertainty principle: the position and momentum of a particle cannot be determined with absolute precision. We discuss the solution of Schrödinger's equation for free particles demonstrating their equivalence with EM phenomena: particles undergo refraction and diffraction, exemplifying the particle/wave duality inherent to QM systems. We discuss QM tunneling and its use in the Scanning Tunneling Microscope. In the following section we study Dirac's equation: the successful attempt by Dirac to unify QM with Einstein's relativity, with the resulting prediction of anti-particles and spin. We then solve for the energy levels of electrons in the hydrogen atom (from Schrödinger's equation) and show that the existence of spin profoundly affects the behavior of electrons in an atom: they cannot share the same energy level, a rule known as Pauli's exclusion principle. Pauli's principle is central to the understanding of the chemical properties of atoms and fully explains Mendeleev's periodic table of the elements. In the next section we discuss along with two exactly soluble systems (diatomic rotational and vibrational levels), various approximations used to study systems (e.g. molecules) for which there are no analytical solutions. In particular, we introduce Pauling's variational approach, Hückel molecular orbital theory and time independent perturbation theory. We apply those approaches to determine the energy levels in alkenes, in multi-electron atoms and in systems under constant electric or magnetic field (such as in Magnetic Resonance Imaging). In the last section we discuss time dependent perturbation theory. We use it to establish the rules allowing for transitions between energy levels and revisit Einstein description of absorption/emission phenomena.