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CRC Press eBooks

The Three-dimensional Schro¨dinger Equations

Alastair I. M. Rae, Jim Napolitano

Published Dec 16, 2015• 0 citations
Publisher

Abstract

In the previous chapter we saw that for a particle in a one-dimensional potential well, physically acceptable solutions to the one-dimensional Schro¨dinger equation are possible only for particular discrete values of the total energy. Moreover, in the case of an electron in a well of atomic dimensions, the spacings between these energy levels are in qualitative agreement with the separations experimentally observed in atoms; we also interpreted the square of the wave function as a probability distribution for the position of the particle. These ideas led us to phenomena, such as quantum-mechanical tunnelling, that have been observed experimentally. The real world, however, is three-dimensional and, although one-dimensional examples often provide useful insights and analogies, we shall have to extend our theory into three dimensions before we can make quantitative predictions of most experimental results. In the present chapter, therefore, we shall set up the three-dimensional Schro¨dinger equation and obtain its solutions in a number of cases, culminating in a discussion of the hydrogen atom where we shall find that theory and experiment agree to a remarkable degree of accuracy.

DOI
10.1201/b19619-17

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In the previous chapter we saw that for a particle in a one-dimensional potential well, physically acceptable solutions to the one-dimensional Schro¨dinger equation are possible only for particular discrete values of the total energy. Moreover, in the case of an electron in a well of atomic dimensions, the spacings between these energy levels are in qualitative agreement with the separations experimentally observed in atoms; we also interpreted the square of the wave function as a probability distribution for the position of the particle. These ideas led us to phenomena, such as quantum-mechanical tunnelling, that have been observed experimentally. The real world, however, is three-dimensional and, although one-dimensional examples often provide useful insights and analogies, we shall have to extend our theory into three dimensions before we can make quantitative predictions of most experimental results. In the present chapter, therefore, we shall set up the three-dimensional Schro¨dinger equation and obtain its solutions in a number of cases, culminating in a discussion of the hydrogen atom where we shall find that theory and experiment agree to a remarkable degree of accuracy.
In the previous chapter, the postulates helped us to use the wave function to find the expected results of experimental measurements by letting a dynamical quantity F (x, p, t) → F (xˆ, pˆ, t) and integrating over space. In the examples, however, the wave functions were typically given and not derived from first principles. We now endeavor to find the appropriate wave functions for a variety of physical systems in one dimension by solving the Schro¨dinger equation where for time-independent cases, the total energy is an eigenvalue. In subsequent chapters, we will extend the method to three dimensions and develop the appropriate operators, eigenvalues, and eigenfunctions for angular momentum. We will also develop methods for examining time-dependent systems. The latter chapters address special systems of interest that may be referred to as applications of quantum mechanics.
In the previous chapters we have seen how solutions to the time-independent Schro¨dinger equation correspond to the allowed energy levels of a quantum system and how, in the hydrogen atom case in particular, the results of this procedure are in extremely good agreement with the results of experiment. It would be possible to extend the process to predict the energy levels of other atoms. We would find that the corresponding Schro¨dinger equations could no longer be solved exactly, but that approximations could be developed which, when combined with computational techniques, would lead to predicted energy levels that were once again in very good agreement with experiment. However, such a programme, most of which is beyond the scope of this book in any case, would be premature at this stage as we have not yet established a general procedure that will do more than predict the allowed energy levels of a particle moving in a potential and the probability that it is in the vicinity of a particular point in space. We do not yet know, for example, how to predict the momentum of an electron in a hydrogen atom; we do not even know if it has a definite value or if it can only be specified by a probability distribution, as is the case for electron position. We have as yet no way of predicting under what conditions an atom undergoes a transition from one state to another, emitting energy in the form of a quantum of electromagnetic radiation.
In the previous chapter we have seen that electrons and other subatomic particles sometimes exhibit properties similar to those commonly associated with waves: for example, electrons of the appropriate energy are diffracted by crystals in a manner similar to that originally observed in the case of x-rays. We have also seen that the energy and momentum of a free particle can be expressed in terms of the angular frequency and wave vector of the associated plane wave by the de Broglie relations (4.8).
Part 1: the need for the quantum mechanics quantization of radiation the special theory of relativity wave-particle duality the nature of matter waves the uncertainty principle the Bohr atom. Part 2 Schrodinger's equation: the postulates of quantum mechanics the wave equation the wave equation in three dimensions the time-independent Schrodinger equation stationary states normalisation probability flux physical constraints on the wave-function wave packets Gaussian wave-packets and the uncertainty principle. Part 3 One-dimensional potential wells: potential wells the one-dimensional infinite square well discussion of infinite square-well results eigenvalue equations the finite square well finite square well eigenfunctions the control of the wave-function by the wave equation numerical integration of Schrodinger's equation continuum solutions of the square-well potential interpretation of unbound-particle wave functions the double potential well the quantum bouncer electric fields and the tilted well the harmonic oscillator - introduction the quantum oscillator discussion of harmonic oscillator eigenvalues and eigenfunctions the classical probability density more potential wells. Part 4 Schrodinger's equation in three dimensions: particle in a three dimensional box degeneracy Schrodingers equation in spherical polar coordinates - the hydrogen atom normalisation. Part 5 Formal development of quantum mechanics: eigenvalues equations, operators and measurements the momentum operator, eigenvalues and eigenfunctions the position operator and its eigenfunctions Hermitian operators orthogonality of eigenfunctions the expansion postulate example - the b-decay of tritium expectation values compatibility of observables - commutators non-commuting operators time-dependence of expectation values - Ehrenfest's theorem abstract operators - the parity operator, matrix mechanics. Part 6 Angular momentum: angular momentum operators angular momentum commutators angular momentum eigenvalues and eigenfunctions interpretation of angular momentum eigenvalues interpretation of angular momentum eigenfunctions the Stern-Gerlach apparatus and electron spin spin operators - the Pauli Spin matrices the Zeeman effect measurements in quantum mechanics. Part 7 Spherically symmetric potential wells: the rigid rotator the radial equation the hydrogen atom and hydrogen like ions the isotropic harmonic oscillator molecular vibrations - the Morse potential the spherical square well general properties of spherically symmetric potential wells. (Part contents)
Tunneling is a supreme quantum effect. Every introductory text [1] on quantum mechanics gives the paradigm example of a particle tunneling through a one-dimensional potential barrier despite having a total energy less than the barrier height. Indeed, the reader typically works through a number of exercises, all involving one-dimensional potential barriers of one form or another modeling several key physical phenomena ranging from atom transfer reactions to the decay of α-particles [2]. However, one seldom encounters coupled multidimenisonal tunneling in such texts since an analytical solution of the Schro¨dinger equation in such cases is not possible. Interestingly, the richness and complexity of the tunneling phenomenon manifest themselves in full glory in the case of multidimensional systems [3]. Thus, for instance, the usual one-dimensional expectation of increasing tunneling splittings as one approaches the barrier top from below is not necessarily true as soon as one couples another bound degree of freedom to the tunneling coordinate. In the context of molecular reaction dynamics, multidimensional tunneling can result in strong mode-specificity and fluctuations in the reaction rates [4]. In fact, a proper description of tunneling of electrons and hydrogen atoms is absolutely essential [5,6] even in molecular systems as large as enzymes and proteins. Although one usually assumes tunneling effects to be significant in molecules involving light atom transfers, it is worth pointing out that neglecting the tunneling of even a heavy atom like carbon is the difference between a reaction occurring or not occurring. In particular, one can underestimate rates by nearly hundred orders of magnitude [7]. Interestingly, and perhaps paradoxically, several penetrating insights into the nature and mechanism of multidimensional barrier tunneling have been obtained from a phase-space perspective [8,9]. The contributions by Creagh, Shudo and Ikeda, and Takahashi in the present volume provide a detailed account of the latest advances in the phasespace-based understanding of multidimensional barrier tunneling.
Quantum mechanics has been enormously successful in explaining the behavior of microsystems such as molecules, atoms, and nuclei. We have seen that quantum mechanics describes a quantum system by the wave function ψ, which is the solution of the Schro¨dinger equation. The wave function determines the probability amplitudes (whose modulus squared gives the probability) for all possible outcomes of a measurement corresponding to an observable on the system. In general, the wave function does not uniquely predict the result of a measurement; it only provides a probability distribution for all possible results of the measurement on a quantum system. Only if the system happens to be in an eigenstate corresponding to the observable being measured, is the result of a measurement of this observable completely predictable. On the other hand, the results of measurements corresponding to a conjugate or non-commuting observable, on the same system in the same state, are indeterminate. Quantum mechanical description of physical systems raises profound questions: How are the wave function and the probabilities for different outcomes of a measurement to be interpreted? Does the wave function represent a single system or an ensemble of systems? Does the physical system actually have the attribute corresponding to the measurement in question or does the measurement itself create the attribute? These questions led to different interpretations of quantum mechanics, which were vigorously debated during the years of its discovery as also in the following decades. The new idea of indeterminacy was especially difficult to reconcile with the long-held view that a physical theory should aim at predicting accurately, and without ambiguity, the result of any measurement on any system, big or small. These debates not only gave us a deeper understanding of quantum mechanics but also changed profoundly the way we view the micro-world.