Chapter 13 is devoted to two important approximation methods used to solve time-independent problems, namely stationary perturbation theory and the variational method. Perturbation theory is developed for both non-degenerate states and degenerate states, with illustrative examples. The Stark effect is considered separately. The dielectric constant of a transparent medium as a function of frequency is shown to result from the modification of the wave function due to the perturbation of the radiation field. Two complementary topics are presented: the canonical transformation method and the Feynman-Hellman method. Finally, the possibilities of the variational method are illustrated by using it first to determine an upper bound for the energy of the stationary states of a quantum system, and then to study more complicated cases, including the partially shielded Coulomb potential produced by a neutral atom.
Chapter 13 is devoted to two important approximation methods used to solve time-independent problems, namely stationary perturbation theory and the variational method. Perturbation theory is developed for both non-degenerate states and degenerate states, with illustrative examples. The Stark effect is considered separately. The dielectric constant of a transparent medium as a function of frequency is shown to result from the modification of the wave function due to the perturbation of the radiation field. Two complementary topics are presented: the canonical transformation method and the Feynman-Hellman method. Finally, the possibilities of the variational method are illustrated by using it first to determine an upper bound for the energy of the stationary states of a quantum system, and then to study more complicated cases, including the partially shielded Coulomb potential produced by a neutral atom.
Perturbation theory for non-degenerate and degenerate systems, variational methods, and WKB approximation are covered in this chapter. First, second, and kth order corrections to energy and wave function ket of non-degenerate states, energy eigenvalues, and wave functions kets of anharmonic oscillator, first-order perturbation theory for degenerate states and linear stark effect are written under perturbation theory. Second part of the chapter includes the variational methods for computation of the energy for ground state of helium atom, Rayleigh-Ritz variational method and its application to hydrogen molecule ion, calculation of energy of excited states, and its application to 1D harmonic oscillator. The topics which are covered under WKB approximation are the classical and non-classical regions of particle motion, alternative derivation of WKB formulae, connecting formulae, and quantum condition for bound state. The kth order corrections to energy and wave function kets for non-degenerate perturbation theory, treatment of WKB approximation from two different approaches and the detailed derivation of connecting formulae, application of variational method to compute energy for excited states are topics which are not generally found in existing text books on quantum mechanics. A good number of solved examples illustrating the importance of approximation methods in contemporary fields are added at the end of chapter.
The subject of perturbation theory in non-relativistic quantum mechanics is introduced. First, perturbation theory for stationary states in the absence of degeneracy is studied. The case of nearby levels, perturbations of a one-dimensional harmonic oscillator, the occurrence of degeneracy, Stark and Zeeman effects are then described in detail. After a brief outline of the variational method, the Dyson series for time-dependent perturbation theory is derived, with application to harmonic perturbations. The Fermi golden rule is also presented. The chapter ends with an assessment of four branches of the subject: regular perturbation theory, asymptotic perturbation theory, and summability methods, spectral concentration and singular perturbations. Approximate methods for stationary states It is frequently the case, in physical problems, that the full Hamiltonian operator H consists of an operator H 0 whose eigenvalues and eigenfunctions are known exactly, and a second term V resulting from a variety of sources (e.g. the interaction with an electric field, or a magnetic field, or the relativistic corrections to the kinetic energy, or the effects of spin). The problems and aims of perturbation theory for stationary states can be therefore summarized as follows. (i) Once the domain of (essential) self-adjointness of the ‘unperturbed’ Hamiltonian H 0 is determined, find on which domain the ‘sum’ H = H 0 + V represents an (essentially) self-adjoint operator (the reader should remember from appendix 4. A that in general, once some operators A and B are given, the intersection of their domains, on which their sum is defined, might be the empty set). […]
Throughout our discussion of the general principles of quantum mechanics we have emphasized the importance of the eigenvalues and eigenfunctions of the operators representing physical quantities. However, we have seen that solving the basic eigenvalue equations determining these is often not straightforward. In the early chapters discussing the energy eigenvalue equation (or time-independent Schro¨dinger equation) for example, we found that this could often not be solved exactly and that, even when a solution was possible, it frequently required considerable mathematical analysis. Because of this, methods have been developed to obtain approximate solutions to eigenvalue equations. One of the most important of such techniques is known as time-independent perturbation theory and will be the first method to be discussed in the present chapter. Another, known as the variational principle, will be discussed later. We shall confine our discussion to the timeindependent Schro¨dinger equation, but generalization to other eigenvalue equations is quite straightforward. We shall mainly use the wave function representation, but we shall restate some of the important results in Dirac notation so that they can be readily transformed to a matrix representation if desired.
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.
This chapter presents approximation methods in quantum mechanics, focusing on both time-independent and time-dependent perturbation theory. The time-independent formulation is developed up to second-order corrections for both nondegenerate and degenerate systems. Applications include the analysis of the Zeeman and Stark effects, where energy level shifts due to magnetic and electric fields are calculated. The time-dependent perturbation theory is introduced, with harmonic perturbations used to derive the first-order transition probabilities and to establish Fermi's golden rule. As an application, the ionization probability of a hydrogen atom under a linearly polarized electromagnetic wave is computed in detail. The treatment is extended to include the case of an unpolarized electromagnetic field. Metadata/Keywords: perturbation theory, Zeeman effect, Stark effect, time-dependent perturbation, harmonic perturbation, Fermi's golden rule, hydrogen ionization