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CRC Press eBooks

- Time-independent Perturbation Theory and the Variational Principle

Alastair I. M. Rae, Jim Napolitano

Published Dec 16, 2015• 0 citations
Publisher

Abstract

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.

DOI
10.1201/b19619-23

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Chapman & Hall/CRC eBooks•Dec 12, 2008•1 citation
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.
The starting point in a quantum mechanical problem is the construction of a Schrödinger equation. We try to solve it exactly to obtain wave function. A Schrödinger equation is exactly solvable only for a certain number of simple potentials. In most of the cases the Schrödinger equation cannot be solved exactly. The solution of the Schrödinger equation for the real systems is usually complicated and often exact solutions are very difficult to find or solutions not exist. Examples include as anharmonic oscillator, hydrogen atom in an electric field, a plane rotator in the presence of an applied electric field and so on. Therefore, we need to rely on approximation methods. The simple and most interesting and powerful approximate method is the perturbation theory developed by Schrödinger in 1926 [1]. Earlier Lord Rayleigh [2] analysed harmonic vibrations of a string perturbed by small inhomogeneities. The work of Rayleigh was pointed out by Schrödinger. Consequently, the method is also called Rayleigh-Schrödinger perturbation theory. This method is powerful for determining the changes in the discrete energy values and the associated eigenfunctions of a system due to a weak perturbation, provided the eigenpairs of the undisturbed system are available. The approximations obtained from the perturbation theory are used to calculate energy level diagrams and to understand the splitting and assignments of atomic and molecular spectra [35]. The perturbation theory has been proven to be useful in several fields of theoretical physics and also in chemistry. It provides considerable insight into various phenomena. The main disadvantage of this method is that in certain problems the perturbation series converges slowly or diverges.
We now consider systems for which the Hamiltonian contains time-dependent interaction terms. In such cases we cannot reduce the time-dependent Schro¨dinger equation to an eigenvalue equation. However, if the time-dependent terms can be regarded as small perturbations, we can develop a form of perturbation theory that can be used to calculate the effects of time-dependent terms. Consider a system for which the Hamiltonian may be written as the sum of a dominant unperturbed part Hˆ0 and a small perturbation Hˆ ′ as Hˆ = Hˆ0 + λHˆ ′(t) , (10.1.1) where the unperturbed Hamiltonian Hˆ0 is independent of time, whereas the perturbation Hˆ ′ may depend on time. The parameter 0 < λ < 1 has been introduced to keep track of various orders of approximations as in the case of time-independent perturbation theory discussed in Chapter 8. The basic idea is that a small perturbation to the Hamiltonian will produce a small change in the wave function. For a time-dependent perturbation, this change means that a system, initially in a particular eigenstate of Hˆ0, will find itself in a time-dependent admixture of the eigenstates. Thus the time-dependent perturbation causes the system to undergo transition to different eigenstates of Hˆ0. So for time-dependent perturbations our interest lies in calculating the probabilities for transition to different states.
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.
Table of Contents 1. The Origins of Quantum Mechanics 1.1 Introduction 1.2 Blackbody Radiation The Problem with Blackbody Radiation 1.3 The Nature of Light The Photoelectric Effect The Compton Effect Is it a Particle or a Wave? 1.4 TheWave Nature of Matter 1.5 The Bohr Atom 1.6 Where do we Stand? 2. Math Interlude A: Complex Numbers and Linear Operators 2.1 Complex Numbers 2.2 Operators Definition of an Operator Eigenfunctions and Eigenvalues 3. The Schrodinger Equation 3.1 Derivation of the Schrodinger Equation 3.2 The Meaning of theWave Function 3.3 The Time-Independent Schrodinger Equation Derivation of the Time-Independent Schrodinger Equation Qualitative Solutions and the Origin of Quantization 4. One-Dimensional Time-Independent Schrodinger Equation 4.1 Unbound States: Scattering and Tunneling Scattering From Step-Function Potentials 4.2 Bound Systems The Infinite SquareWell The Harmonic Oscillator Potential 5. Math Interlude B: Linear Algebra 5.1 Properties of Linear Operators 5.2 Vector Spaces Inner Products Adjoint and Hermitian Operators Basis Sets 6. The Three-Dimensional Time-Independent Schrodinger Equation 6.1 Solution in Rectangular Coordinates 6.2 Angular Momentum 6.3 The Schrodinger Equation in Spherical Coordinates 6.4 The Hydrogen Atom 7. Math Interlude C: Matrices, Dirac Notation, and the Dirac Delta Function 7.1 The Matrix Formulation of Linear Operators 7.2 Dirac Notation 7.3 The Dirac Delta Function 8. Spin Angular Momentum 8.1 Spin Operators 8.2 Evidence for Spin 8.3 Adding Angular Momentum 8.4 The Matrix Representation of Spin 8.5 The Stern-Gerlach Experiment 8.6 Spin Precession 8.7 Spin Systems with Two Particles Noninteracting Spins Interacting Spins 8.8 Measurement Theory Hidden Variables The ManyWorlds Interpretation of Quantum Mechanics 9. Time-Independent Perturbation Theory 9.1 Derivation of Time-Independent Perturbation Theory 9.2 Perturbations to the Atomic Energy Levels Fine Structure The Lamb Shift 9.3 The Atom in External Electric or Magnetic Fields The Atom in an Electric Field: The Stark Effect The Atom in a Magnetic Field: The Zeeman Effect 10. The Variational Principle 10.1 Variational Principle: Theory 10.2 Variational Principle: Application to the Helium Atom 11. Time-Dependent Perturbation Theory 11.1 Derivation of Time-Dependent Perturbation Theory 11.2 Application: Selection Rules for Electromagnetic Radiation 12. Scattering Theory 12.1 Definition of the Cross Section 12.2 The Born Approximation 12.3 PartialWaves 13. The Multiparticle Schrodinger Equation 13.1 Wave Function for Identical Particles 13.2 Multielectron Atoms 14. Some Modern Applications of Quantum Mechanics 14.1 Magnetic Resonance Imaging 14.2 Quantum Computing 15. What Comes Next? Relativistic Quantum Mechanics 15.1 The Klein-Gordon Equation Derivation of the Klein-Gordon Equation Probability Densities and Currents 15.2 The Dirac Equation Answers and Hints for Selected End-of-Chapter Exercises Index
In the previous chapters, we have solved a series of problems that all have an exact solution. However, there are only a select few problems in quantum mechanics that provide exact analytical solutions. Those problems that can be solved exactly are the free particle, the one-dimensional barrier potential, the finite and the infinite square wells, the infinite triangular well, the harmonic oscillator, and the hydrogen atom, including both its nonrelativistic and relativistic solutions. However, there are many problems different from the above-mentioned few as well as problems that cannot be approximated by these solutions. What happens then if we want to solve a different problem, such as the helium atom or the hydrogen atom in an applied electric field? To solve these problems it is necessary to use approximation techniques. In this chapter, we consider some of these techniques, the most important being the time-independent and the time-dependent perturbation theories. We begin with a discussion of time-independent disturbances in a nondegenerate system. Time-independent Perturbation Theory: The Nondegenerate Case We seek to determine the solution to a problem in which a small disturbance is applied to an otherwise determinable system. Perturbation theory is used most often in cases for which the solution to the undisturbed (unperturbed) system is known and the perturbation is small. For example, perturbation theory is useful in solving for the energy levels in a hydrogen atom in the presence of a small external electric field.
We have seen that to determine the possible energies En (energy eigenvalues) which a physical system can have and the corresponding eigenfunctions (wave functions) ψn, we have to set up and solve the time-independent Schro¨dinger equation Hψn = Enψn . (8.1.1) In this equation, the wave function ψn, representing the n-th eigenstate of the system in the coordinate representation, is a function of the continuously varying eigenvalues of the position observables of the system, the number of position observables being equal to number of degrees of freedom of the system. The Hamiltonian operator H, in the coordinate representation, is a differential operator involving the continuously varying eigenvalues of the position observables and the derivatives with respect to them. Since we will be dealing with the operators mostly in the coordinate representation, we shall denote them without the caret.