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
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
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.
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). […]
Equivalent derivations of time-dependent pertubation theory; Fermi golden rule; the Born approximation for scattering from Fermi golden rule; survival probability of a state in a time-independent perturbation; positronium in static and oscillating magnetic fields; hydrogen atom in a time-dependent electric field; a model for inelastic scattering of a projectile with a target; semiclassical treatment of the electromagnetic field; ionization of the hydrogen atom by an electromagnetic wave; cross sections for stimulated absorption and emission in hydrogen; spontaneous emission and selection rules with an application to the 2p to 1s transition in hydrogen; theory of the line width; formal scattering theory; S- and T-operators.
How to deal with time-dependent potentials, what kinds of physical problems having time-dependent potentials can be solved exactly and which are to be solved with the use of perturbation theory, what are different possible forms of time-dependent perturbating fields, and semi-classical treatment of the interaction of fields with matter are the subject matters of this chapter. First order perturbation theory, computation of transition probability, transition rates and Fermi's Golden Rule for harmonic and constant perturbations, absorption, stimulated emission and dipole approximation when electromagnetic fields interact with matter, spontaneous emission and Einstein coefficients, and dipole selection rules are other topics which are dealt with in detail in the chapter. Discussions with properly justified mathematical treatment on time-dependent potentials and on the exactly solvable time-dependent two-state systems are the special foci of this chapter.
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.
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.