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 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.
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
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). […]
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.
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.
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.
Abstract This review presents time-independent perturbative methods for solving the one-dimensional Schrödinger equation, highlighting representative cases that reveal key aspects of the theory. The focus is on their relevance to quantum computing applications, particularly in systems with finite-dimensional state spaces. The main link between these methods and quantum processing emerges when we consider systems with only a finite number of well-defined energy levels, e.g., two levels corresponding to the ‘zero’ and ‘one’ states of a quantum bit (qubit), for which the Schrödinger equation describes a quantum algorithm corresponding to the unitary evolution of the qubits. Perturbative techniques can then be applied to this evolution to gain deeper insight into the algorithm or to simplify it in a controlled manner, as described in the last sections of this review. We initially discuss representative applications using benchmark cases that exemplify the essential features of perturbation theory while avoiding unnecessary technical complications. The methods presented involve direct approaches to solutions for quantum systems with small potential perturbations, with consideration of indirect and approximation techniques. Key cases examined include the particle in a potential well, the harmonic oscillator, and systems with polynomial or Dirac delta distribution perturbations, each chosen to highlight unique aspects of perturbative analysis. Starting with an overview of the unperturbed Schrödinger equation, we derive canonical solutions and then use perturbative techniques to approximate energy shifts and wavefunction corrections in both non-degenerate and degenerate settings. By combining theoretical discussion with case studies, this review underscores how perturbative methods are applied across a range of elementary quantum mechanical problems especially for applications in the qubit model, which, in many cases of interest, can be reduced to the explicit calculations shown here.