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Reports on Progress in Physics

Quantum-mechanical perturbation theory

John P. Killingbeck

Published Sep 1, 1977• 163 citations
Publisher

Abstract

Modern computers have made possible the evaluation of higher order terms of perturbation series. Apart from the empirical work involving numerical calculations, much formal mathematical work has been done on the convergence properties of perturbation series and of Pade approximants which represent them. Some of the modern work in perturbation theory is reviewed in the context of traditional results from the theory of real and complex variables. The two major versions of time-independent perturbation theory, the Rayleigh-Schrodinger (RS) and Brillouin-Wigner (BW) theories, are compared and contrasted, and the alternative techniques for evaluating the terms in the energy series are discussed. The sum-over-states method, the differential equation method and the variational principle method are treated, with emphasis on their inter-relations.

DOI
10.1088/0034-4885/40/9/001

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Modern computers have made possible the evaluation of higher order terms of perturbation series. Apart from the empirical work involving numerical calculations, much formal mathematical work has been done on the convergence properties of perturbation series and of Pade approximants which represent them. Some of the modern work in perturbation theory is reviewed in the context of traditional results from the theory of real and complex variables. The two major versions of time-independent perturbation theory, the Rayleigh-Schrodinger (RS) and Brillouin-Wigner (BW) theories, are compared and contrasted, and the alternative techniques for evaluating the terms in the energy series are discussed. The sum-over-states method, the differential equation method and the variational principle method are treated, with emphasis on their inter-relations.
Rayleigh-Schrödinger time-independent perturbation theory is a key method in quantum mechanics for solving problems where the Hamiltonian of a quantum system cannot be exactly solved. By expanding the solutions in series, this method allows one to obtain approximations for quantum states and eigen-energies, especially for systems where the interactions or perturbing forces are small compared to the principal part of the Hamiltonian. This is crucial for understanding complex phenomena, predicting the behaviours of atomic and molecular systems, and calculating corrections to basic theoretical models, thereby improving the accuracy of quantum predictions. In this work, we will show that using the unitary operators, we arrive at the equations giving the different order of corrections of both energy as well as wave functions of the time-independent perturbation theory. Our approach closely mirrors the famous formalism of Rayleigh-Schrodinger perturbation theory (RSPT). The use of unitary operators simplifies the derivation of higher-order corrections, making the process more accurate and accessible to researchers. This technique harnesses the potential of unitary operators within a perturbation series framework. By combining these two powerful techniques, we offer a comprehensive framework for addressing normalization challenges in quantum mechanical calculations. This methodology not only facilitates a deeper understanding of perturbation theory but also serves as a pedagogical stepping stone, encouraging postgraduate researchers to apply their foundational knowledge and acquired skills in practical problem-solving situations with confidence. This is therefore a second proof or a new method to derive the fundamental equations of Rayleigh Schrodinger perturbation Theory RSPT using the unitary transformations.
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.
A perturbation theory is described which leads to two alternative methods for calculating the eigenvalues and normalized eigenstates of a perturbed Hamiltonian, the results being given to all orders in the perturbation. The expansions obtained are formulated in terms of two sets of partial sums which have simple, easily characterized forms, and they combine some of the advantages of both the Rayleigh-Schr\"odinger and Brillouin-Wigner perturbation methods while avoiding some of the difficulties of each. In particular, one form of the perturbation expansions given here will in most cases of interest have a larger radius of convergence than the Rayleigh-Schr\"odinger series. As is usual for infinite-order treatments, the explicit form of the final result applies only to nondegenerate levels. However, some of the intermediate relations obtained in the derivation are of general validity. Since certain classes of unlinked diagrams appear in the expansions, the method described here is not suitable for application to systems containing a large number of particles.
Abstract In this chapter we review time-independent and time-dependent perturbation theory in quantum mechanics. We begin with Rayleigh-Schrödinger perturbation theory for small corrections to the Hamiltonian for non-degenerate and degenerate spectra, which leads us to a discussion of avoided crossings. We then apply these methods to calculate the fine-structure corrections for the energy levels of the hydrogen atom, including the relativistic correction to the kinetic energy, the spin-orbit correction, and the Darwin term. We then turn to the effect of weak constant magnetic fields: for the resulting Zeeman effect we distinguish between the anomalous Zeeman effect and the Paschen-Back effect. In the context of the corresponding Stark effect for electric fields we introduce the Wigner-Eckart theorem and calculate perturbations to first and second order. We then turn to time-independent problems and discuss the Born-von Neumann series for the propagator, time-ordered integrals, the interaction picture, before explaining Fermi’s golden rule.
Abstract The theory of perturbations of electronic systems has been considered by various writers, and the method is the basis of the solution of most quantum problems. It therefore seems desirable that the theory should be placed on a firm footing, and this necessitates the discussion of the convergence of the series of perturbations, which up to the present has been avoided. This investigation is all the more necessary since the wave equation of the Stark Effect has no solution of the form assumed by Schrödinger in his original discussion of the perturbation theory. Dirac’s theory leads to a system of linear differential equations in an infinite number of variables, and 2 is devoted to the discussion of the existence theorem for such a system by a matrix method. In 3 the application is made to the perturbation theory in the case of perturbations satisfying the conditions assumed in 2. In 4 the theory is extended so as to include more general types of disturbances. It is shown that, though the series of perturbations does not in general converge, yet it usually possesses the same asymptotic character as in the classical theory, and its use can therefore be justified.