This chapter begins by exploiting the Einstein–de Broglie relation and the notion of symbol, as defined in Eq. (3.6.6). The following steps are the local and global conservation laws associated to the Schrödinger equation, the probabilistic interpretation of the wave function, the spreading of wave packets and transformation properties of wave functions. The solution of the Schrödinger equation for a given initial condition is then studied. For this purpose, one first expands the initial condition in terms of eigenfunctions of the Hamiltonian operator. This is then ‘propagated’ to determine the evolution of the wave function. Thus, one is led to consider the Green kernel of the Schrödinger equation, and the boundary conditions on the wave function that lead to complete knowledge of stationary states. A dynamics involving an isometric non-unitary operator is also studied. The chapter ends with an elementary introduction to harmonic oscillators and to the JWKB method in wave mechanics, plus examples on the Bohr–Sommerfeld quantization. From classical to wave mechanics The correspondence between differential operators and polynomials in k relies on the notion of the symbol defined in Eq. (3.6.6). Now we are aiming to pass from a function on phase space, i.e. the classical Hamiltonian, to an operator which, by analogy, is called the Hamiltonian operator. Such a transition is non-trivial because the map from symbols to operators contains some ambiguity. Such a transition is always possible if polynomials in p have constant coefficients. When this is not the case, i.e. if the coefficients are functions on the configuration space, there is an obvious ambiguity in the association of an operator with xp or px , for instance.
This chapter begins by exploiting the Einstein–de Broglie relation and the notion of symbol, as defined in Eq. (3.6.6). The following steps are the local and global conservation laws associated to the Schrödinger equation, the probabilistic interpretation of the wave function, the spreading of wave packets and transformation properties of wave functions. The solution of the Schrödinger equation for a given initial condition is then studied. For this purpose, one first expands the initial condition in terms of eigenfunctions of the Hamiltonian operator. This is then ‘propagated’ to determine the evolution of the wave function. Thus, one is led to consider the Green kernel of the Schrödinger equation, and the boundary conditions on the wave function that lead to complete knowledge of stationary states. A dynamics involving an isometric non-unitary operator is also studied. The chapter ends with an elementary introduction to harmonic oscillators and to the JWKB method in wave mechanics, plus examples on the Bohr–Sommerfeld quantization. From classical to wave mechanics The correspondence between differential operators and polynomials in k relies on the notion of the symbol defined in Eq. (3.6.6). Now we are aiming to pass from a function on phase space, i.e. the classical Hamiltonian, to an operator which, by analogy, is called the Hamiltonian operator. Such a transition is non-trivial because the map from symbols to operators contains some ambiguity. Such a transition is always possible if polynomials in p have constant coefficients. When this is not the case, i.e. if the coefficients are functions on the configuration space, there is an obvious ambiguity in the association of an operator with xp or px , for instance.
This chapter begins by exploiting the Einstein–de Broglie relation and the notion of symbol. The following steps are the local and global conservation laws associated with the Schrödinger equation, probabilistic interpretation of the wave function and probability distribution, the spreading of wave packets and transformation properties of wave functions. In the last part, the Heisenberg picture is outlined at an introductory level. From classical to wave mechanics In the previous chapter we have seen how to go from wave equations on space–time to Hamilton equations on phase space by means of an appropriate approximation requirement on wave solutions. In more formal language, we could say we have considered a procedure to associate a Hamiltonian ordinary differential equation on phase space starting with a partial differential equation on configuration space. This association produces a correspondence between differential operators and polynomials on phase space, which relies on the notion of symbol (see below). Now we are aiming to pass from a function on phase space, i.e. the classical Hamiltonian, to an operator which, by analogy, is called the Hamiltonian operator. Such a transition is physically non-trivial because it amounts to building a wave equation from the equation on rays. From the formal point of view it appears to contain some ambiguities. Such a transition is always possible if polynomials in p have constant coefficients.
In the past few chapters, the Schrödinger equation has been developed and applied to the solution of a number of quantum mechanical problems, mainly to develop experience with the results of simple and common systems. The results from these examples can be summarized relatively simply. In general, quantization enters the problem through the non-commuting nature of conjugate operators such as position and momentum as well as from classical boundary quantization. This has led to the Schrödinger equation itself being the primary equation of motion for the wave function solution to the problem. In essence, duality is incredibly important and is the basic method by which the electron is treated as a wave, rather than as a particle, and the wave equation of interest is the Schrödinger equation. When boundary conditions are applied, either through potential barriers or through the form of the potential (as in the harmonic oscillator), the time-independent Schrödinger equation yields solutions that are often special functions. Examples of this are the sines and cosines in the rectangular-barrier case, the Airy functions in the triangular-well case, and the Hermite polynomials in the harmonic oscillator case.
A physics-oriented review is first given of wave equations: examples, the Cauchy problem, solutions in various coordinates, their symmetries, how to build a wave packet. Fourier analysis and dispersion relations are then introduced, and here the key tool is the symbol of differential operators, which makes it possible to study them in terms of algebraic polynomials involving cotangent-bundle variables. Further basic material deals with geometrical optics from the wave equation, phase and group velocity (and their dual relationship in momentum space), the Helmholtz equation and the eikonal approximation for the scalar wave equation. The Schrödinger equation is then derived with emphasis on the wave packet and its relation to classical behaviour in the light of the Einstein–de Broglie relation. For this purpose, it is shown that it is possible to build a wave packet for which the wave-like properties manifest themselves for distances of the order of atomic dimensions. The Fourier transform with respect to time of the wave packet obeys the stationary Schrödinger equation, while the wave function is found to obey a partial differential equation which is of first order in time. The wave equation The wave equation occurs in several branches of classical physics, e.g. the theory of sound, electromagnetic phenomena in vacuum and in material media, and elastic vibrations of material bodies. We consider first the simplest situation, i.e. the propagation of waves in a homogeneous, isotropic and stationary medium. Propagation is characterized by the refractive index n , a quantity that is independent of the point in space-time.
We found in the previous chapter that the molecular partition function is required to determine the thermodynamic properties of an ideal gas. To evaluate the partition function, specification of pertinent energy levels and degeneracies is necessary. Such knowledge demands that we investigate at least the rudiments of quantum mechanics, and especially those quantum concepts required for subsequent applications to statistical thermodynamics. For this reason, we concentrate in the next few chapters on the Schrödinger wave equation, whose various solutions provide the ε j 's and g j 's needed for the eventual calculation of thermodynamic properties. Depending on your academic background, you might thus consider reviewing classical mechanics (Appendix G) and operator theory (Appendix H) in preparation for your upcoming study of quantum mechanics. We begin this chapter with a historical review of the developments leading to the formulation of quantum mechanics, subsequently focusing on the Bohr model for atomic hydrogen and the de Broglie hypothesis for matter waves. We then introduce the Schrödinger wave equation, the basic postulates of quantum mechanics, and salient insights from these postulates germane to the development of statistical thermodynamics. We next apply the Schrödinger wave equation to the translation energy mode of an atom or molecule. This application conveniently explains both quantum states and quantum numbers, including their relation to our previous notions of microstate and macrostate. We end this chapter by discussing the Heisenberg uncertainty principle, including its utility in defining indistinguishability and symmetry conditions for multiparticle systems.
The commutator of position and momentum operators is first considered in the coordinate and momentum representations, and then in an abstract Hilbert space. The reader is then introduced to canonical operators with the associated canonical quantization of commutation rules, which consists of maps defined on a symplectic space and taking values in the set of unitary operators on a Hilbert space. If the symplectic space is finite-dimensional, all of its irreducible representations are unitarily equivalent. The Weyl exponentiated form of the commutation relations is described and investigated. One then arrives at the definition of Weyl systems, and it is shown how to recover from them the formulation in terms of self-adjoint operators which satisfy a generalized form of commutation relations. Further topics are the Heisenberg representation for temporal evolution and the generalized uncertainty relations. Unitary operators associated with symplectic linear transformations are then considered, and, within this framework, translations, rotations and the harmonic oscillator are considered. The Weyl programme is then reassessed. Lastly, the basic postulates of modern quantum theory are eventually studied: the probabilistic nature of the predictions of results of measurements; the correspondence between observables and self-adjoint operators on Hilbert spaces; the expected result of measuring an observable quantity; and the evolution of the state vector in systems which are not affected by any external influence. The chapter ends with an outline of rigged Hilbert space formalism and its applications. The commutator in wave mechanics In the first part of this book we studied wave mechanics within the framework of the Schrödinger equation.
Abstract The second chapter introduces the notion of wave functions and their equation of motion proposed by Erwin Schrödinger. The interpretation and normalization of the wave function are discussed, leading to the continuity equation. The chapter also introduces basic mathematical operations that can be carried out for wave functions and operators, describing e.g., how to calculate scalar products and commutators, as well as expectation values and variances of observables. With these tools at hand, Heisenberg’s uncertainty principle is re-examined, focusing on the example of a Gaussian wave packet, which is studied both in position space and momentum space. We also discuss the time evolution of general states and of the exemplary wave packet. Finally, we will see how classical physics is recovered as a limiting case of the quantum-mechanical description