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    Quantum Mechanics: Principles and Formalism
    Quantum Mechanics: Principles and Formalism
    Quantum Mechanics: Principles and Formalism
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    Quantum Mechanics: Principles and Formalism

    By Roy McWeeny

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    Concerned strictly with the principles and formalism of quantum mechanics, this graduate student-oriented volume develops the subject as a fundamental discipline. Opening chapters review the origins of Schrödinger's equations and the nature of the solutions in certain simple and well-known cases, advancing to the ideas associated with vector spaces. Having provided students with the appropriate mathematical language, the author proceeds to the formulation of the main principles of quantum mechanics and their immediate consequences. The book concludes with final generalizations in which alternative "languages" or representations are discussed — each with reference to its specific advantages and applications — and the Dirac transformation theory is developed and explained.
    LanguageEnglish
    PublisherDover Publications
    Release dateMay 23, 2012
    ISBN9780486143804
    Quantum Mechanics: Principles and Formalism

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      Quantum Mechanics - Roy McWeeny

      INDEX

      PREFACE

      Note: The following Preface reflects the fact that this book, now reprinted separately, was first published as part of The International Encyclopedia of Physical Chemistry and Chemical Physics.

      NO MAJOR work covering the general area of Chemical Physics would be complete without a substantial section on quantum mechanics. Quantum mechanics provides not only the physical principles and mathematical methods used in all theoretical work on the electronic structure and properties of matter; it provides even the concepts and vocabulary of nearly all branches of theoretical chemistry. It is therefore of some importance to indicate the aims and scope of this section of the Encyclopedia, distinguishing clearly between quantum mechanics as a discipline and quantum mechanics applied to chemical problems.

      Quantum mechanics is here developed as a fundamental discipline. Although applications are frequently considered, they are introduced only to illustrate principles or give point to the development of the subject in various directions. More detailed applications of quantum mechanics—to atomic structure, molecular binding, molecular properties, solid state theory, and so on—are found in other sections of the Encyclopedia.

      Each volume is severely restricted in length, covering a well-defined area at a fundamental level and exhibiting a considerable degree of independence so as to be useful as a textbook in its own right. Another prerequisite is that the exposition shall not be so severe as to overtax the resources of good graduate students in physics or chemistry, though clearly topics of intrinsic mathematical difficulty will be heavy reading for students whose mathematical skills are rudimentary.

      With these limitations in mind it seemed necessary to plan for at least four short volumes on (non-relativistic) quantum mechanics. The first would confine itself to an exposition of the basic principles and formalism, illustrated mainly by reference to the simplest possible one-particle systems. The second would develop the main techniques—such as perturbation theory, and group theory—in the context of basic applications, again as far as possible with reference to a single particle moving in some given field: it would give point to the theory by introducing the independent particle model, in which each electron moves in an effective field provided by the others, and in this way would serve to indicate the applicability of quantum mechanics to atoms, molecules and crystals. The third would deal quite generally with many-electron systems, introducing specifically many-body topics such as permutation symmetry, vector coupling, electron correlation, and would include general theory of electronic properties. The fourth would return to the basic principles and formalism, particularly those referring to time-dependent effects, and develop the more elementary parts of the theory of scattering and collisions. Each volume would thus be relatively compact and suitable for use either by itself or in conjunction with the others, according to the particular interests or background of the reader. Further volumes would no doubt be added as the pressure of new developments and applications, for example in more advanced collision theory, made them necessary.

      The present volume is accordingly concerned with the principles and formalism of quantum mechanics. It is not strictly an introduction to the subject, since all graduate students in physics and chemistry can nowadays confidently be expected to have some acquaintance with quantum mechanics at its most elementary level. Chapters 1 and 2 merely review the origins of Schrödinger’s equations and the nature of the solutions in certain simple and well-known cases. Matters which are extraneous to the subject (e.g. standard methods of separating and solving partial differential equations) are relegated to Appendices so as not to interrupt the development. The ideas associated with vector spaces, however, and more generally with Hilbert space, are so much a part of the whole fabric of quantum mechanics that they have been developed in Chapter 3 as an essential part of the text. This chapter provides the mathematical language with which it is possible to formulate the main principles and their immediate consequences in Chapter 4. Special attention has been given to the more difficult topics, such as spin, which are frequently skipped, glossed over or presented in an abstruse and unpalatable form. This chapter leads naturally to the final generalizations (Chapter 5) in which various alternative languages or representations are discussed—each with its own advantages in particular applications—and the Dirac transformation theory is developed and explained.

      Any author of yet another book on quantum mechanics must expect criticism. A mathematical physicist may complain that the delta function has been introduced too casually, or that the Lagrangian formalism has not been given due prominence, or that continuing controversies about the measurement process have been largely ignored. Many a chemist, on the other hand, may object to so many pages on vector spaces and mathematical techniques. But the book is addressed specifically to neither of these readers. In Volume 1 I have tried to present the main principles of the theory with special regard to the needs of chemical physicists, recognizing that present work in such diverse fields as electron spin resonance, molecular beam experiments, and Compton scattering brings with it the need for much sophisticated analysis, and a familiarity with the Heisenberg representation, momentum space, and all the trappings of the general theory. If this and succeeding volumes can bring the theory and its current applications in chemical physics within the reach of a good graduate student they will fulfil their main object.

      Finally, I wish to thank Professor K. Ohno (University of Hokkaido) for his help in the early planning of the first two volumes, which were started several years ago under joint authorship. Although distance and the pressure of other commitments prevented the full fruition of this collaboration, his contributions, and particularly his critical and constructive comments on most of the present volume in a semi-final form, are gratefully acknowledged. My thanks are also due to Mrs. S. P. Rogers for her careful and accurate production of the typescript, and to Pergamon Press for their co-operation at all times.

      R. McW.

      CHAPTER 1

      PHYSICAL BASIS OF QUANTUM THEORY

      1.1. Particles and waves

      There is little doubt that the most concise and elegant exposition of the principles of quantum mechanics consists of a set of basic propositions, from which the whole theory may be derived without further appeal to experiment. The experimental basis of the subject is in this way absorbed into a set of postulates which, although by no means self evident, lead to a network of conclusions which may be tested and verified. The postulates consequently provide a very succinct expression of the results of a wide range of observations. From these postulates, it is possible in principle, though often difficult in practice, to follow the ramifications of the theory into many branches of physics and chemistry.

      In spite of the many attractions of the axiomatic approach, to which we return in Chapter 4, it is useful first to recall some of the basic observations concerning wave and particle behaviour of light and electrons. These led to the generalizations on which the more formal theory is based. To this end, some familiarity with the wave-particle dualism will be assumed. We recall two of its main features:

      (A) There is evidence (e.g. from the photo-electric effect and the Compton effect) that radiation exhibits particle properties. It appears to be transmitted in localized packets with energy E and momentum p related to frequency v in the following way:

      (1.1)

      (1.2)

      Here c is the velocity of light, h is Planck’s constant;

      A light particle with energy given by (1.1) and momentum by (1.2) is called a photon.

      (B) There is evidence (e.g. from electron-diffraction experiments) that material particles exhibit wave properties. The relative frequency with which particles are found in a given region of space (measured, for example, by the intensity of darkening of a photographic plate on which a beam of particles falls) is found to be correctly predicted as the squared amplitude of a wave-like disturbance, propagated according to laws formally similar to those of physical optics. For particles travelling in a beam, with a constant velocity, the associated wave is plane and has its normal in the direction of motion. It was suggested by de Broglie, on the basis of relativistic considerations, that the wave length should be related to the particle momentum p = mv by

      (1.3)

      which agrees exactly with (1.2) since λ = c/v, and this conjecture was subsequently verified experimentally.

      Wave mechanics, the particular formulation of quantum mechanics due to Schrödinger, arose in the attempt to reconcile the apparent coexistence of wave-like and particle-like properties in both material particles and photons. Here we indicate the argument, in a rudimentary form, by considering a harmonic wave travelling in the positive x direction:

      (1.4)

      where ψ measures the magnitude of the disturbance at point x and time t and u is the velocity of propagation.

      We remember the interpretation of k. If x increases by 1/k, the values of ψ and its derivatives are unchanged: the disturbance is therefore periodic in space, at any given time, with period λ = 1/k. λ is the wave length and k is the wave number. Also if t increases by 1/(ku), ψ and its derivatives are again unchanged: the disturbance is therefore periodic in time at any given point in space, with period T = 1/(ku). T is the period of a complete oscillation, its reciprocal v = ku being the frequency of oscillation. The definitions are thus

      Also, the two functions (1.4) (either choice of sign) clearly oscillate only between maximum and minimum values ± A; A is the amplitude. A disturbance which is everywhere real can of course be regarded as the real part of either function, or as the sum of the two since eiθ = cos θ + i sin θ.

      Wave packets

      According to Fourier’s theorem, any disturbance, travelling to the right with velocity u, can be represented by combining waves such as (1.4) with variable k values and suitably chosen amplitudes:

      (1.5)

      which is the limit-of a sum of terms

      A1 exp {2πik1(x−ut)} + A2 exp {2πik2(x − ut)} + ...

      as the values of k1, k2, ... get closer together until they cover the whole range (− ∞, + ∞),¹ the amplitude then becoming a continuous function of k. An arbitrary disturbance which is everywhere real can always be represented in this form by suitably choosing the amplitudes; thus by taking just two terms with k1 = − k2 = k and A1 = A2 we obtain a travelling wave with ψ ∝ cos 2πk(x−ut). Equivalently, we may simply take the real part of an expression of the form (1.5).

      We now try to obtain a localized disturbance—suitable for associating with a moving particle—by choosing the amplitude factor A(k) so that the wave trains admitted interfere constructively at one point but destructively at all others. A wave packet of this kind can in fact be constructed by using a very narrow range of wave numbers and may therefore be virtually homogeneous in frequency. If radiation (or matter) were propagated in wave packets, each packet could thus correspond to a sharply specified frequency and yet be essentially localized like a particle. To illustrate this possibility we consider a Gaussian wave packet in which

      (1.6)

      When σ is large this will describe a superposition of wave trains with wave numbers differing inappreciably from k0, the amplitudes falling off rapidly according to the Gaussian law. In this case,

      (1.7)

      From the well-known result

      (1.8)

      (which is valid when p and q are complex, provided the real part of p is positive), it follows easily that

      (1.9)

      At t = 0, this describes an oscillation of wave length λ0 = 1/kexp( − π²x²/σ) is rapidly damped about the point x = 0 (Fig. 1.1a).

      In the case of a photon, u = c (the velocity of light) is constant in free space. The packet is then propagated without dispersion (i.e. change of shape) for ψ(x, t) at time t has exactly the same form as ψ(x, 0) except that x is replaced by x−ct, i.e. the pattern is shifted to the right through a distance ct (Fig. 1.1b). The frequency ck0, from which the waves in the packet deviate inappreciably, is presumably related to the photon energy by the Planck law (1.1), and the photon, identified with the wave packet, travels with velocity c.

      FIG. 1.1. Motion of a wave packet: (a) initial form (t = 0), (b) form at time t.

      In the case of a material particle, it might seem natural to relate the frequency of an associated wave train to the particle energy in the same way as for a photon, namely by the Planck law. But the fact that λ is known to depend on the particle momentum, according to de Broglie’s relationship (1.3), then implies that the velocity of propagation, u = λv, is no longer a constant but depends on the dynamical situation. We tentatively accept this implication and combine (1.1) and (1.3) to obtain (since p = mv )

      (1.10)

      where E is the total energy of the particle, and V its potential energy in the field in which it moves. The velocity of propagation then depends on frequency (through E) and, when the potential is non-uniform, on the particle position (through V). In this case dispersion occurs as the wave packet is propagated, and it is necessary to distinguish two velocities: u is now referred to as the phase velocity, but no longer coincides with the velocity of the packet itself, i.e. the velocity of the point at which the component waves reinforce. The wave packet moves with the group velocity, vg, which may differ considerably from u.

      We now show that by accepting (1.10) we ensure that vg exactly coincides with the particle velocity v. We again consider the Gaussian packet (1.7) but now admit dispersion by assuming a non-linear relationship between k and v, as would follow from

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