The physics community was now faced with two theories of quantum phenomena which could scarcely have differed more radically from one another and yet both had achieved remarkable successes in explaining precisely the same physical phenomena – the spectral lines of the hydrogen atom, the zero point energy of quantum systems, the quantisation of the harmonic oscillator, the quantum rotator and the Stark effect. Furthermore, both theories could account for the experimental data, unlike the predictions of the old quantum theory. Perhaps these quite different approaches are not so surprising when it is appreciated that matrix and wave mechanics started from the diametrically opposite poles of the wave–particle duality. At the heart of the Heisenberg approach was the fundamental role played by the non-commutative behaviour of the quantum variables and the quantisation of both the momentum and spatial variables. To accommodate these features, a new mathematical calculus had been invented from the realisation that matrices followed precisely the correct algebraic rules. The elaboration of this scheme led to the concept of the energy levels of a quantum system being associated with the diagonalisation of matrices using the eigenvalue procedure. As Jammer remarks, the theory ‘… defied any pictorial representation; it was an algebraic approach which, proceeding from the observed discreteness of spectral lines, emphasised the element of discontinuity ; in spite of its renunciation of classical description in space and time it was ultimately a theory whose basic conception was the corpuscle .’
The physics community was now faced with two theories of quantum phenomena which could scarcely have differed more radically from one another and yet both had achieved remarkable successes in explaining precisely the same physical phenomena – the spectral lines of the hydrogen atom, the zero point energy of quantum systems, the quantisation of the harmonic oscillator, the quantum rotator and the Stark effect. Furthermore, both theories could account for the experimental data, unlike the predictions of the old quantum theory. Perhaps these quite different approaches are not so surprising when it is appreciated that matrix and wave mechanics started from the diametrically opposite poles of the wave–particle duality. At the heart of the Heisenberg approach was the fundamental role played by the non-commutative behaviour of the quantum variables and the quantisation of both the momentum and spatial variables. To accommodate these features, a new mathematical calculus had been invented from the realisation that matrices followed precisely the correct algebraic rules. The elaboration of this scheme led to the concept of the energy levels of a quantum system being associated with the diagonalisation of matrices using the eigenvalue procedure. As Jammer remarks, the theory ‘… defied any pictorial representation; it was an algebraic approach which, proceeding from the observed discreteness of spectral lines, emphasised the element of discontinuity ; in spite of its renunciation of classical description in space and time it was ultimately a theory whose basic conception was the corpuscle .’
‘In spite of its high-sounding name and its successful solutions of numerous problems in atomic physics, quantum theory, and especially the quantum theory of polyelectron systems, prior to 1925, was, from the methodological point of view, a lamentable hodgepodge of hypotheses, principles, theorems and computational recipes rather than a logical consistent theory. Every single quantum-theoretic problem had to be solved first in terms of classical physics; its classical solution had then to pass through the mysterious sieve of the quantum conditions or, as it happened in the majority of cases, the classical solution had to be translated into the language of quanta in conformance with the correspondence principle. Usually, the process of finding the ‘correct solution’ was a matter of skillful guessing and intuition, rather than of deductive or systematic reasoning.’ (Jammer, 1989) Although written with the benefit of hindsight, there is no doubt that, by the end of 1924, there was a major crisis in the attempts to create a system of ‘quantum mechanics’ which could encompass all the features of atoms and their spectra. At the heart of the problem was the wave–particle duality first enunciated by Einstein in 1905 and reinforced by de Broglie's remarkable association of ‘matter-waves’ with electrons in 1924. As recorded by Jammer (1989), ‘This state of affairs was well characterised by Sir William Bragg when he said that physicists are using on Mondays, Wednesdays, and Fridays the classical theory and on Tuesdays, Thursdays and Saturdays the quantum theory of radiation.’
Abstract The new quantum mechanics consists of a scheme of equations which are very closely analogous to the equations of classical mechanics, with the fundamental difference that the dynamical variables do not obey the commutative law of multiplication, but satisfy instead the well-known quantum conditions. It follows that one cannot suppose the dynamical variables to be ordinary numbers (c-numbers), but may call them numbers of a special type (q-numbers). The theory shows that these q-numbers can in general be represented by matrices whose elements are c-numbers (functions of a time parameter). When one has performed the calculations with the q-numbers and obtained all the matrices one wants, the question arises how one is to get physical results from the theory, i. e., how can one obtain c-numbers from the theory that one can compare with experimental values ? Hitherto this has been done with the help of a number of special assumptions. In Heisenberg’s original matrix mechanics it was assumed that the elements of the diagonal matrix that represents the energy are the energy levels of the system, and the elements of the matrix that represents the total polarisation, which are periodic functions of the time, determine the frequencies and intensities of the spectral lines in analogy to the classical theory. Schrodinger’s wave representation of the quantum mechanics has provided new ways of obtaining physical results from the theory, based on the assumption that the square of the amplitude of the wave function can in certain cases be interpreted as a probability. From this assumption one can, for instance, work out the probability of a transition being produced in a system (or the number of transitions produced in an assembly of like systems) by an arbitrary external perturbing force, and can thus, by supposing the perturbation to consist of incident radiation, obtain directly Einstein’s B coefficients. Again in Born’s treatment of collision problems it is assumed that the square of the amplitude of the wave function scattered in any direction determines the probability of the colliding electron (or other body) being scattered in that direction.
Abstract The development of quantum theory was driven by a consistently repeated failure of classical physics to accommodate the results of ever more sophisticated experiments on the microphysical world of radiation, elementary particles, atoms, and molecules. Each break-through in the development of the theory’s conceptual structure was followed (sometimes very rapidly) by new experimental data that just did not fit, pointing to the need for yet further refinements. As is typical in such a radical change in the approach to acquiring scientific understanding, old and often unsuitable concepts were forced into service to meet the needs of the new description. Confusion reigned. The major figures in the theory’s early development took up radically different positions on the theory’s interpretation, and, as we will see, the debate became polarized in ways that remain relevant today.
In 1926, Schrödinger [365] recognized that the variational theory of elliptical differential equations with fixed boundary conditions could produce a discrete eigenvalue spectrum in agreement with the energy levels of Bohr's model of the hydrogen atom. This conceptually startling amalgam of classical ideas of particle and field turned out to be correct. Within a few years, the new wave mechanics almost completely replaced the ad hoc quantization of classical mechanics that characterized the “old” quantum theory initiated by Bohr. Although the matrix mechanics of Heisenberg was soon shown to be logically equivalent, the variational wave theory became the standard basis of methodology in the physics of electrons. The nonrelativistic Schrödinger theory is readily extended to systems of N interacting electrons. The variational theory of finite N -electron systems (atoms and molecules) is presented here. In this context, several important theorems that follow from the variational formalism are also derived.
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.
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.