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CRC Press eBooks

The One-dimensional Schro¨dinger Equations

Alastair I. M. Rae, Jim Napolitano

Published Dec 16, 2015• 0 citations
Publisher

Abstract

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).

DOI
10.1201/b19619-16

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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).
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 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.
According to non-relativistic quantummechanics, the evolution of the wave function of a free particle of mass m and momentum p is described by the Schro¨dinger equation: i ∂ψ ∂t = Hψ , (6.1) with the Hamiltonian operator H = −∇2/2m obtained from the expression for energy E = p2 2m , (6.2) using the substitution E → i ∂ ∂t , p → −i∇ . (6.3) Schro¨dinger himself [6] first suggested a generalisation of equation (6.1) based on the use of the relativistic energy equation: E2 = p2 +m2 . (6.4) (+m2)ψ = 0 , (6.5) Multiplying by ψ∗ and subtracting the product of ψ and the complex conjugate of (6.5) from the result, the continuity equation is obtained ∂ρ ∂t = ∇j , (6.6) with ρ = ψ∗ ∂ψ ∂t − ψ∂ψ ∂t (6.7) and j = −∇ (ψ∗∇ψ − ψ∇ψ∗) . (6.8) However, the ρ which appears in equation (6.6) cannot be identified with the probability density, in analogy with the similar quantity obtained from the Schro¨dinger equation, because it does not have the required property of being always positive-definite. To be convinced of this it is sufficient to substitute i∂/∂t→ E in (6.7). The result, ρ = E|ψ|2 , shows that ρ can be either positive or negative, following from the fact that the Klein-Gordon equation has solutions for the energy with both signs E = ± √ p2 +m2 , Note that in the non-relativistic limit E ≈ m > 0, and the familiar result ρ ∝ |ψ|2 is recovered.
In his extremely important paper [1] E. Schro¨dinger proposed a wave equation which is the basic equation of the “undulatorical” mechanics and can be considered as a substitution to the Hamilton-Jacobi partial differential equations (HJ) of the ordinary (classical) mechanics. The wave equation was established on condition that the Lagrange function contains no terms linear in velocities. Schro¨dinger writes (footnote on p. 514 l.c.): “In relativistic mechanics and in the case of a magnetic field the expression of the (HJ) is more complicated. In the case of a single electron this equation means the constancy of the four-dimensional gradient diminished by a given vector (the four-dimensional potential). The wave mechanical translation of this Ansatz meets some difficulties.”
This chapter discusses the conceptual foundations of quantum mechanics in the context of matter. Classical physics identified matter with particles and radiation with "waves." Although this description accounted for a large number of very important facts, it became apparent around the turn of the century that other phenomena, such as blackbody radiation and photoelectric effect, are satisfactorily explained only if radiation is described in terms of particles. Sometime later the hypothesis that, conversely, matter has wave properties was proposed by Louis de Broglie and was confirmed by the Davisson-Germer experiment of electron diffraction. In this experiment and similar ones, an electron beam was passed through a regular lattice (crystal), and subsequently showed the well-known diffraction patterns that are characteristic of waves. These results confirmed the theoretical predictions that a monoenergetic electron beam should be described by a plane wave and that the wave vector k of the wave should be related to the momentum p of an individual electron.