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CRC Press eBooks

The Quantized Harmonic Oscillator: Vibrational Spectroscopy

Don Shillady

Published Jul 27, 2011• 0 citations
Publisher

Abstract

Now that we have learned some of the principles which apply in quantum mechanics, we move on to the next more difficult problem of a quantized harmonic oscillator. The goal here is to provide a rigorous application of the polynomial method of solving differential equations on a relatively simple case and to provide some insight into how the Schrödinger equation was first solved [1]. Then we proceed to application in the form of worked examples. We have tried to give sufficient details of this solution to allow a student to follow the derivation with pencil and paper but do not forget to ponder over the spectroscopic applications! This author would agree that it is more important to absorb the main conclusions of this material than to master the derivations. In fact, the highest recommendation of this author is to always ask ‘‘What does this mean?’’ and absorb the conclusions for a future activity called ‘‘thinking’’ rather than just memorizing facts.

DOI
10.1201/b12869-18

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Now that we have learned some of the principles which apply in quantum mechanics, we move on to the next more difficult problem of a quantized harmonic oscillator. The goal here is to provide a rigorous application of the polynomial method of solving differential equations on a relatively simple case and to provide some insight into how the Schrödinger equation was first solved [1]. Then we proceed to application in the form of worked examples. We have tried to give sufficient details of this solution to allow a student to follow the derivation with pencil and paper but do not forget to ponder over the spectroscopic applications! This author would agree that it is more important to absorb the main conclusions of this material than to master the derivations. In fact, the highest recommendation of this author is to always ask ‘‘What does this mean?’’ and absorb the conclusions for a future activity called ‘‘thinking’’ rather than just memorizing facts.
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.
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.
The study of quantum properties of the harmonic oscillator is important in physics as many real-world systems oscillate harmonically. Motion of systems in a confined space is often modeled as being a quantized harmonic motion or, in first instance, is approximated by a harmonic motion. This chapter helps the reader to solve the equation employing an algebraic operator technique, which is based on the Dirac notation. This approach has several definite advantages and exploits the commutation relations among the operators involved and their properties. The chapter transforms the stationary Schrodinger equation into a second-order differential equation and finds the solution to the equation with the aid of a more advanced mathematical technique that involves special functions. The energy of a harmonic oscillator is quantized, with the sequence of values. The difference in energy between adjacent energy levels is equal to the energy of a single photon, ħω.
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.