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CRC Press eBooks

Quantum Mechanics Approximate Methods

Lukong Cornelius Fai

Published Apr 19, 2022• 0 citations
Publisher

Abstract

In quantum mechanics, there exist a lot of problems from the domain of atomic, molecular, solid-state physics, physics of magnetic phenomena, nuclear physics, etc. The number of problems which may be solved exactly are few such as some one-dimensional problems, problems in the rectangular well (barrier), the oscillator, problems of motion in a central field such as motion in a Coulomb field. These methods are well formulated and are used in evaluations to a greater approximation. However, in some cases, these may create problems that are very difficult, if not impossible, to be solved exactly. In such problems, the Hamiltonian cannot be exactly diagonalized in a simple manner. For such problems, we resort to approximate methods for finding the eigenvalues and eigenfunctions of the Hamiltonian. Besides, these approximate methods yield results closer to experimental ones. Amongst the approximate methods, we examine the variational method.

DOI
10.1201/9781003273073-9

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•Aug 29, 2026•0 citations
In quantum mechanics, there exist a lot of problems from the domain of atomic, molecular, solid-state physics, physics of magnetic phenomena, nuclear physics, etc. The number of problems which may be solved exactly are few such as some one-dimensional problems, problems in the rectangular well (barrier), the oscillator, problems of motion in a central field such as motion in a Coulomb field. These methods are well formulated and are used in evaluations to a greater approximation. However, in some cases, these may create problems that are very difficult, if not impossible, to be solved exactly. In such problems, the Hamiltonian cannot be exactly diagonalized in a simple manner. For such problems, we resort to approximate methods for finding the eigenvalues and eigenfunctions of the Hamiltonian. Besides, these approximate methods yield results closer to experimental ones. Amongst the approximate methods, we examine the variational method.
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.
As in classical mechanics the number of exactly soluble quantum mechanical problems is very limited and in most cases of practical interest numerical techniques and approximation methods are unavoidable. The availability of fast computers has turned quantum computation into a major industry. This chapter looks at the several approximation techniques. In seeking to solve the Schrodinger equation with the perturbed Hamiltonian, it is convenient to work with series expansions by introducing a dimensionless parameter λ. In many cases the system of interest differs from an exactly soluble system by only a small disturbance, enabling an approximation to be made by expanding in powers of a smallness parameter. The Variational Method provides a very simple method of approximating energy eigenvalues. It is most useful for computing ground state energies and its success depends on our being able to make a reasonable guess for the form of the ground state wave function.
In most cases solving a quantum mechanical problem exactly is not always possible. In such a case, an analytic solution to the Schrödinger equation is appropriate. This results to numerical solutions that may not necessarily be the best approach. Interest sometimes may not necessarily be in the detailed eigenfunctions, but rather in the energy levels and the qualitative features of the eigenfunctions. So, the numerical solutions are usually less intuitively reasonable. It is possible to find the values of the energy levels to be slightly sensitive to the deviation of the wave function from its true form. So, the expectation value of the energy for an approximate wave function can be a very good estimate of the corresponding energy eigenvalue. Using an approximate wave function dependent on some set of variational parameters and minimizing its energy by these variational parameters yield such energy estimates. This technique is the so-called variational method due to this minimization procedure.
The starting point in a quantum mechanical problem is the construction of a Schrödinger equation. A Schrödinger equation is exactly solvable only for a certain number of simple potentials. In most of the cases the Schrödinger equation can be solved exactly. The solution of the Schrödinger equation for the real systems is usually complicated and often exact solutions. 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. The splitting of an energy level due to the interaction of the nuclear magnetic dipole and the magnetic field Be produced by the electron orbit current is called the fine structure. The term hyperfine structure is used to describe extremely small splitting of spectral lines.
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.
Exactly solvable quantum systems are rare—the harmonic oscillator, the hydrogen atom, the square well—and the physics of everything else is the physics of approximation. This article presents a narrative review of the primary literature that built quantum mechanics' approximation methods, from Rayleigh's Theory of Sound, whose treatment of slightly perturbed vibrating systems gave perturbation theory its name and scheme, and Ritz's 1909 variational method, which converted boundary-value problems into energy minimizations, through Schrödinger's 1926 wave mechanics, which equipped the new quantum theory with perturbation theory from the start, Born and Oppenheimer's 1927 adiabatic separation of electronic and nuclear motion, the 1926 papers of Wentzel, Kramers, and Brillouin that independently derived the semiclassical expansion bearing their initials, Hartree's 1928 self-consistent field and Hylleraas's 1929 variational computation of helium, which made the many-electron atom calculable, Kato's 1949 mathematical foundation of the perturbation method's convergence, Landau and Lifshitz's codifying textbook, and Bender and Wu's 1969 demonstration that the anharmonic oscillator's perturbation series diverges—the asymptotic character that defines the method's limits. The synthesis is organized around three themes: the perturbation program, in which small parameters turned the solvable cases into engines for the unsolvable; the variational program, in which upper bounds and trial functions turned minimization into the many-body atom's working instrument; and the semiclassical bridge, in which the WKB expansion connected wave mechanics to action-angle quantization and exposed tunneling. It is concluded that the three programs are complementary solutions to one problem—the gap between what can be solved and what must be calculated—and that their asymptotic character, made precise by Bender and Wu, is not a defect but the field's realistic self-understanding.