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BENTHAM SCIENCE PUBLISHERS eBooks

Approximation Methods for Bound States

Iraj R. Afnan

Published Apr 14, 2011• 0 citations
Publisher

Abstract

With a limit on the small number of problems that admit exact solutions, we turn in this chapter to approximation methods that can be used for bound state problems. The most commonly used method is the perturbation theory for which one use a small parameter to form the basis of a systematic expansion, or a variational method in which one hopes to set the best limit on the energy of a system. We will consider both of these approximation methods with applications to problems in atomic and molecular physics.

DOI
10.2174/978160805250911101010252

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With a limit on the small number of problems that admit exact solutions, we turn in this chapter to approximation methods that can be used for bound state problems. The most commonly used method is the perturbation theory for which one use a small parameter to form the basis of a systematic expansion, or a variational method in which one hopes to set the best limit on the energy of a system. We will consider both of these approximation methods with applications to problems in atomic and molecular physics.
As in classical mechanics the number of exactly soluble quantum mechanical problems is very limited and in most cases of practical interest numerical techniques and approximation methods are unavoidable. The availability of fast computers has turned quantum computation into a major industry. This chapter looks at the several approximation techniques. In seeking to solve the Schrodinger equation with the perturbed Hamiltonian, it is convenient to work with series expansions by introducing a dimensionless parameter λ. In many cases the system of interest differs from an exactly soluble system by only a small disturbance, enabling an approximation to be made by expanding in powers of a smallness parameter. The Variational Method provides a very simple method of approximating energy eigenvalues. It is most useful for computing ground state energies and its success depends on our being able to make a reasonable guess for the form of the ground state wave function.
In chapters 13 and 14 we focused on perturbation theories for time-independent and time-dependent perturbations. For time-independent perturbations we obtained first-order and second-order corrections to energy eigenvalues and eigenfunctions. For time-dependent perturbations we obtained the probability for a system to make a transition from an ith initial state to fth final state. We have also discussed how to study the effect of adiabatic and sudden perturbations. In the present chapter we consider the variational method. The variational method can be used to construct an approximate ground state eigenfunction. In some cases the method can be used for finding approximately the energy of first few discrete states of a bound system. The perturbation theory uses a set of unperturbed states and the perturbation Hamiltonian H(1) to construct the eigenfunctions and eigenvalues through highly formalized approximations. In contrast, the variational method is based on a guess for the state-a trial state which is used to determine the corresponding energy. Any well behaved trial state introduced will yield an appropriate energy, although some trial states will be better than other, but whatever the guess, we can always make systematic improvements. We can construct a reasonably accurate eigenfunction often by a physical insight and ingenuity.
In this chapter, we present some fundamental issues about approximation methods that are often used when a quantum-mechanical system is perturbed and about the relationship between classical and quantum mechanics. In Sec. 10.1 we introduce the stationary perturbation theory, while Sec. 10.2 is devoted to time-dependent perturbations. In Sec. 10.3 we briefly examine the adiabatic theorem. In Sec. 10.4 we introduce the variation method, an approximation method that is not based on perturbation theory. In Sec. 10.5 we discuss the classical limit of the quantum-mechanical equations, whereas in Sec. 10.6 we deal with the semiclassical approximation, in particular the WKB method. On the basis of the previous approximation methods in Sec. 10.7 we present scattering theory. Finally, in Sec. 10.8 we treat a method that has a wide range of applications: the path-integral method. Stationary perturbation theory Perturbation theory is a rather general approximation method that may be applied when a small additional force (the perturbation) acts on a system (the unperturbed system), whose quantum dynamics is fully known. If the disturbance is small, it modifies both the energy levels and the stationary states. This allows us to make an expansion in power series of a perturbation parameter, which is assumed to be small. Perturbation theory may be applied both to the case where the additional force is time-independent (in which case a stationary treatment suffices – the subject of the present section) as well as to the case where it explicitly depends on time.
The solution of most problems associated with electron quantum states in physical systems and structures (atoms, molecules, quantum nanostructure objects, and crystals) is hard to find because of the mathematical difficulties of getting exact solutions of the Schrödinger equation. Therefore, approximate methods of solving such problems are of special interest. We will consider some of these methods, such as the adiabatic approximation now and later the effective-mass method , using real physical systems as examples. In this chapter we will consider several widely used approximation methods for finding the wavefunctions and energies of quantum states as well as the probabilities of transitions between quantum states. First of all, we will consider stationary and non-stationary perturbation theories. What is common to these two theories is that it is assumed that the perturbation is weak and that it changes negligibly the state of the unperturbed system. Stationary perturbation theory is used for the approximate description of a system's behavior if the Hamiltonian of the quantum system being considered does not directly depend on time. In the opposite case, non-stationary theory is used. Then, we will briefly consider the quasiclassical approximation, which is used for the problems of quantum mechanics which are close to analogous problems of classical mechanics. Stationary perturbation theory for a system with non-degenerate states This theory is used for the approximate calculation of the energy levels and the wavefunctions of stationary states of systems that are subjected to the influence of small perturbations.
Synopsis: It is rare that exact solutions for physical quantum systems are available, and likely that one or more types of perturbation theories need to be applied. ƒree time-independent, or static, methods are discussed. Using exact energy shift formulas, a result correct to second order for the perturbed system energy is derived and applied to a two-state system and a harmonic oscillator example. ƒe WKB semiclassical approximation is motivated, and applications to barrier penetration and various types of bound-state problems are made. ƒe third class of methods gives upper limit estimates of system ground-state properties based on energy functional variations.
Synopsis: It is rare that exact solutions for physical quantum systems are available, and likely that one or more types of perturbation theories need to be applied. Three time-independent, or static, methods are discussed. Using exact energy shift formulas, a result correct to second order for the perturbed system energy is derived and applied to a two-state system and a harmonic oscillator example. The WKB semiclassical approximation is motivated, and applications to barrier penetration and various types of bound-state problems are made. The third class of methods gives upper limit estimates of system ground-state properties based on energy functional variations.