We begin with some examples of one-dimensional vibration in a nonparabolic potential chosen to permit complete analytical solution of Schrödinger's time-independent equation. These examples are of isochronous vibrators which classically have a frequency independent of amplitude, and which might be expected therefore to have energy levels equally spaced at a separation of ħω 0 . This expectation turns out to be very nearly right and inspires a certain confidence in the semi-classical procedure developed by (among others) Bohr, Wilson and Sommerfeld. We therefore apply this procedure to some non-isochronous systems and find once more rather good agreement with the results of exact quantum mechanics. Periodic systems in fact can often be treated semi-classically with adequate accuracy, and significant economy of effort in comparison with strict quantum-mechanical analysis. This approach pays handsomely when we turn in the next chapter to the quantization of electron cyclotron orbits which, as already discussed in chapter 8, are closely related to harmonic oscillators. Conduction electrons in semi-conductors, and still more in metals, have their behaviour modified by the lattice through which they move, and a complete quantal treatment has never been achieved. It is clear, however, from approximate calculations, often of great complexity, that the semiclassical method describes most of the interesting physical processes correctly and very simply. In chapter 15 we shall describe in outline some of the effects which can be treated quite well enough for most purposes without even writing down Schrödinger's equation.
We begin with some examples of one-dimensional vibration in a nonparabolic potential chosen to permit complete analytical solution of Schrödinger's time-independent equation. These examples are of isochronous vibrators which classically have a frequency independent of amplitude, and which might be expected therefore to have energy levels equally spaced at a separation of ħω 0 . This expectation turns out to be very nearly right and inspires a certain confidence in the semi-classical procedure developed by (among others) Bohr, Wilson and Sommerfeld. We therefore apply this procedure to some non-isochronous systems and find once more rather good agreement with the results of exact quantum mechanics. Periodic systems in fact can often be treated semi-classically with adequate accuracy, and significant economy of effort in comparison with strict quantum-mechanical analysis. This approach pays handsomely when we turn in the next chapter to the quantization of electron cyclotron orbits which, as already discussed in chapter 8, are closely related to harmonic oscillators. Conduction electrons in semi-conductors, and still more in metals, have their behaviour modified by the lattice through which they move, and a complete quantal treatment has never been achieved. It is clear, however, from approximate calculations, often of great complexity, that the semiclassical method describes most of the interesting physical processes correctly and very simply. In chapter 15 we shall describe in outline some of the effects which can be treated quite well enough for most purposes without even writing down Schrödinger's equation.
By the time a student of physics is ready to tackle quantum mechanics he has become familiar with the classical harmonic vibrator through many examples, and knows the crucial role it played in the development of Planck's ideas. It is natural then to concentrate on the mathematical aspects of the harmonic oscillator equation in quantum mechanics, the solution of Schrödinger's equation, normalization of the wave-function, calculation of mean values and of matrix elements, leaving the physics to look after itself. At a more advanced level the harmonic vibrator provides the entry into field theories, second quantization etc., and as a general rule it tends to be viewed more as a vehicle for instruction in more interesting matters than as a physical system having its own considerable interest and importance. Here we shall seek to redress the balance and study the vibrator as a thing in itself, without losing sight of the variety of physical problems to which the results can be applied. One especially important set of applications, however, will get little attention at this stage – the vibrations of compound bodies and of extended physical systems provide such wealth of interest as to justify a volume to themselves; and it is to such matters that the whole of the third part of this work will be devoted. As soon as one begins to contemplate the harmonic vibrator one becomes aware of the exceptional nature of its behaviour, in that it conforms more closely than any other system to the classical rules.
As is appropriate in an exposition of the quantum mechanics of vibrators, we started with a quantal calculation and have finished with one; but we have never strayed far from the classical models. We began, indeed, in chapter 13 the task of establishing limits to the validity of classical reasoning, and the very last example of this chapter has been used to demonstrate, somewhat perversely it might be thought, that the method of quantum mechanics can occasionally be applied to systems which physicists and engineers would instinctively regard as classical. So long as the discussions give insight into physical processes and reveal the strengths and weaknesses of the analytical tools available, no apology is needed and no defence is offered except the evidence of the book itself. Even the rather simple systems which provide material for the whole of the volume demonstrate clearly the increased power available to those who can handle both classical and quantal reasoning. The reader who wishes to apply his skill to complex vibratory processes will find his tasks eased if he can use whichever seems advantageous at each stage, and be confident that his understanding of simple processes will enable him to recognize the dangers inherent in both approaches – the danger of carrying classical reasoning too far into the quantum domain, and the danger of forcing over-simplifications on physical systems to make them amenable to the unforgiving methodology of quantum mechanics.
Abstract It is a common practice to approach quantum mechanics through the study of a few, exactly soluble examples using the Schrödinger equation in position-space. The number of potential energy functions for which such closed-form solutions are available is, however, quite small. Luckily, many of them actually correspond reasonably well to actual physical systems; examples include the infinite well as a model of a free particle ina “box “ (Chapters 5 and 7), the harmonic oscillator (Chapter 9), the rigid rotator (Chapter 16), and the Coulomb potential for the hydrogen atom (Chapter
This chapter begins with a discussion of radiation by a microscopic classical oscillator with radiative damping. It then turns to the Schrödinger equation for the hydrogen atom, and an extended analysis of the solutions to the Schrödinger equation for the hydrogen atom in polar coordinates is then presented. Real orbitals are constructed from linear combinations of the complex Schrödinger equation solutions. The significance of real orbitals for molecular structure and the consequent introduction of rotating and vibrating dipoles are then introduced. A semiclassical model (quantal atom and classical E-M field) for the absorption and emission of radiation is developed and compared to the Einstein A and B coefficients. It is shown how the time-dependence of the radiatively coupled non-stationary states of the hydrogen atom are analogous to the classical harmonic oscillator. The essentials of atomic transitions, as well as molecular rotational, vibrational, and electronic spectroscopy complete the chapter.
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.
After this excursion into the field of non-linear vibrators, we now return to the harmonic vibrator and take up a point which had begun to reveal itself at the end of chapter 13, where we found that under the influence of a uniform, but arbitrarily time-varying, force the vibrator never forgets its initial state. If it started in the ground state, for ever afterwards its response can be described by the movement of a compact distribution in the σ-representation of equivalent classical vibrators; only the centroid of the distribution responds to the applied force. The harmonic vibrator is thus extraordinarily resistant to randomization. To be sure, if the force is not uniform, but depends on the displacement of the oscillating particle, the result just summarized is no longer true. Nevertheless, in the most important application, where an oscillator of atomic dimensions is influenced by electromagnetic vibrations, the force due to the electric field is as nearly uniform as makes no difference, since the wavelength of electromagnetic waves at a typical atomic resonant frequency is a thousand times the size of an atom. The disturbing aspect of the resistance of a vibrator to randomization is that in all theories of black-body radiation, before and after Planck, it is assumed that material oscillators and electromagnetic vibrations in a cavity will eventually share the chaotic state that allows statistical mechanics to be applied.