The objective of this chapter is to go over a few of the basic concepts of quantum mechanics in preparation for a discussion of spectroscopy, which is in many ways the business end of quantum mechanics, at least for chemical scientists. We will also need a few quantum mechanical ideas from time to time in our study of thermodynamics and of kinetics. Why should we learn quantum mechanics at all? Atoms and molecules are small, and their constituent parts, electrons, protons and neutrons, are even smaller. Early in the twentieth century, we learned that small things don't obey the laws of classical mechanics. A different kind of mechanics, quantum mechanics, is required to understand chemistry on a fundamental level. In fact, we need different mechanical theories to treat extremes of both size and speed. Figure 2.1 summarizes the situation. There isn't a sharp cut-off between the various sectors of this diagram. Also note that some of the theories are more general than others. We could in principle use quantum mechanics or general relativity to predict the trajectories of tennis balls, but it just isn't worth the effort, given that classical mechanics works perfectly well in this range of masses and speeds. On the other hand, classical mechanics doesn't give very good results for things that are either extremely large, or small, or fast. Like it or not, to discuss phenomena on an atomic scale, we need quantum mechanics. Ordinary (non-relativistic) quantum mechanics is generally adequate, although electrons in heavy atoms sometimes reach relativistic speeds (approaching the speed of light, c ), requiring relativistic quantum mechanics.
The objective of this chapter is to go over a few of the basic concepts of quantum mechanics in preparation for a discussion of spectroscopy, which is in many ways the business end of quantum mechanics, at least for chemical scientists. We will also need a few quantum mechanical ideas from time to time in our study of thermodynamics and of kinetics. Why should we learn quantum mechanics at all? Atoms and molecules are small, and their constituent parts, electrons, protons and neutrons, are even smaller. Early in the twentieth century, we learned that small things don't obey the laws of classical mechanics. A different kind of mechanics, quantum mechanics, is required to understand chemistry on a fundamental level. In fact, we need different mechanical theories to treat extremes of both size and speed. Figure 2.1 summarizes the situation. There isn't a sharp cut-off between the various sectors of this diagram. Also note that some of the theories are more general than others. We could in principle use quantum mechanics or general relativity to predict the trajectories of tennis balls, but it just isn't worth the effort, given that classical mechanics works perfectly well in this range of masses and speeds. On the other hand, classical mechanics doesn't give very good results for things that are either extremely large, or small, or fast. Like it or not, to discuss phenomena on an atomic scale, we need quantum mechanics. Ordinary (non-relativistic) quantum mechanics is generally adequate, although electrons in heavy atoms sometimes reach relativistic speeds (approaching the speed of light, c ), requiring relativistic quantum mechanics.
Because atoms and molecules are small, their behavior can only be understood using quantum mechanics, rather than classical mechanics. Quantum mechanics amounts to studying the behavior of electrons and nuclei and their interactions. We will limit ourselves to slowly moving electrons and nuclei, and thus will not need to discuss relativistic quantum mechanics. Large particles also obey quantum mechanics, but the relevant wavelengths are so small that we don't notice them. Small particles absolutely require the use of quantum mechanics for any meaningful understanding. This treatment is not merely an inconvenience: it leads to useful and interesting phenomena such as the Pauli exclusion principle, the Aufbau principle, Hund's rules, the Heisenberg uncertainty principle, wave-particle duality, the photoelectric effect, Ehrenfest's theorem, and the correspondence principle.
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 deals with the behaviour of matter and light on the atomic and subatomic scale. It attempts to describe and account for the properties of molecules and atoms and their constituents--electrons, protons, neutrons, and other more esoteric particles such as quarks and gluons. Its concepts frequently conflict with common-sense notions derived from observations of the everyday world. Quantum mechanics has attracted some of the ablest scientists of the 20th century, and they have erected what is perhaps the finest intellectual edifice of the period. Quantum mechanics is concerned with phenomena that are so small-scale that they cannot be described in classical terms. The history of quantum mechanics may be divided into three main periods. The first began with Planck's theory of black-body radiation in 1900; it may be described as the period in which the validity of Planck's constant was demonstrated but its real meaning was not fully understood. The second period began with the quantum theory of atomic structure and spectra proposed by Niels Bohr in 1913. True quantum mechanics appeared in 1926, reaching fruition nearly simultaneously in a variety of forms--namely, the matrix theory of Max Born and Werner Heisenberg, the wave mechanics of Louis V. de Broglie and Erwin Schrodinger, and the transformation theory of P.A.M. Dirac and Pascual Jordan.
Quantum theory To conceptualize the molecular origins of thermodynamic equilibrium, one must first understand the elemental ways by which molecules interact. How does the world really work? What are the most fundamental principles that form the basis of reality as we know it? Currently our understanding of reality rests upon two principal concepts in physics: quantum theory and relativity. Both of these have been subjected to stringent experimental tests over the past century, and their combination has in part led to a deep understanding of elementary particles. There still remain some incompatibilities between the two, namely in understanding the nature of gravity, and there have been intense efforts to find new fundamental physical explanations. However, for the purposes of our discussion, we will focus solely on quantum theory since for nearly all of the models and systems that we will discuss one can safely avoid considerations of relativistic effects. Quantum mechanics describes the complete time evolution of a system in a quantum sense, in a manner analogous to what Newtonian mechanics does for classical systems. It is most easily described in terms of a system of fundamental particles, such as electrons and protons.
There is no dissent regarding the quantum theory success on the small-scale structure of the world but there is equally an open subject of debate about its interpretation. Both quantum mechanics and the theory of relativity are indeed extensions of classical mechanics, that is, they reproduce their results in other appropriate limiting cases. Quantum mechanics provides a new set of laws and a method of description of microscopic systems that has been very successful. The chapter discusses some of the fundamental principles of this highly controversial subject. In quantum physics, it is difficult to uphold a sharp distinction between the object and the observer. The chapter examines why quantum mechanics seems to be so hard for newcomers to learn and understand. The theory of quantum mechanics has led to many applications: laser, the electron microscope and many other technological devices.