This paper discusses some practical problems in quantum mechanics, particularly finding solutions of the Schrödinger equation for some cases, as it is a pivotal part of this area. The article focuses on using perturbation theory to calculate the approximate ground state energy for both helium atom and quartic anharmonic oscillator. For the helium atom, conventional perturbation theory is used to solve for the approximate energy, whilst for the anharmonic oscillator, a slightly different approach, that is perturbation theory incorporating a parameter, is chosen to improve the precision of the approximation. The final relative errors for the ground state energy of helium atom model are, for the first order perturbation, , and for the second order, , and that for the anharmonic oscillator is . The study of perturbation theory gives insights into understandings of how it may be modified further to pursue a better level of precision. This facilitates development of new approximation techniques for solving quantum-mechanical issues.
This paper discusses some practical problems in quantum mechanics, particularly finding solutions of the Schrödinger equation for some cases, as it is a pivotal part of this area. The article focuses on using perturbation theory to calculate the approximate ground state energy for both helium atom and quartic anharmonic oscillator. For the helium atom, conventional perturbation theory is used to solve for the approximate energy, whilst for the anharmonic oscillator, a slightly different approach, that is perturbation theory incorporating a parameter, is chosen to improve the precision of the approximation. The final relative errors for the ground state energy of helium atom model are, for the first order perturbation, , and for the second order, , and that for the anharmonic oscillator is . The study of perturbation theory gives insights into understandings of how it may be modified further to pursue a better level of precision. This facilitates development of new approximation techniques for solving quantum-mechanical issues.
In this article, for pedagogical purposes we have discussed the application of nondegenerate perturbation theory up to the third order to compute energy eigenvalues and wave functions for the quantum anharmonic oscillator. Energy levels of a single quartic oscillator for 𝜆 values in range of 0.1-1 are given. Perturbed and non-perturbed wave functions of the levels up to the fourth excited level are compared. Ground, first and second excited energy levels are also calculated by applying finite differences method and, results are compared with the ones obtained via perturbation theory. It is found that perturbation theory gives comparable results only for a small 𝜆 parameter and for the ground state. The quartic term in the Hamiltonian of the anharmonic oscillator leads to a more effective confinement of the particle which is deduced from the plots of wavefunctions and probability distributions. Meanwhile, the number of zero crossing nodes of the wavefunctions increases as the energy level increases, which is an expected result for both the harmonic and anharmonic oscillator.
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.
This is an investigation of the energy levels and wavefunctions of an anharmonic oscillator characterised by the potential 1/2 (omega 2 q 2 + lambda q 4 ). As a lowest-order approximation an extremely simple formula for energy levels, E i (0) = (i + 1/2)1/4(3/alpha i + alpha i ), is derived (i being the quantum number of the energy level), which covers any (lambda, i). alpha i is the real positive root of a cubic equation: y i alpha i 3 + alpha i 2 - 1 = 0, with y i = 6lambda(2i 2 + 2i + 1)/(2i+1). This formula reproduces the exact energy levels within an error of about 1% for any ( lambda ,i) (the worst case is 2% for i = 0, lambda to infinity). Systematically higher orders of this perturbation theory are developed, which contains the 'usual' perturbation theory for the limiting case of small lambda , but this perturbation theory is valid for any (i, lambda). The second-order perturbation theory reduces the errors of our lowest-order results by a factor of about 1/5 in general. Various ranges (large, intermediate, small) of (i, lambda ) are investigated and compared with the exact values obtained by the Montroll group (1975, 1978). For i = 0, 1, even the fourth-order perturbation calculation can be elaborated explicitly, which reduces the error to about 0.01% for any lambda . For small lambda it gives correct numerical coefficients up to lambda 4 terms, as it should.
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.
This report discusses two new ideas for using perturbation methods to solve the time-independent Schrödinger equation. The first concept begins with rewriting the perturbation equations in a form that is closely related to matrix diagonalization methods. That allows a simple, compact derivation of the standard (Rayleigh-Schrödinger) equations. But it also leads to a new iterative solution method that is not based on the usual power series expansion. The iterative method can also be used when the unperturbed system is two-fold degenerate. The second concept is quite different from the first but compatible with it. It is based on the fact that one can replace the true Hamiltonian with a synthetic Hamiltonian having the same eigenvalues. This approach allows one to cancel part of the perturbation and to reduce the size of the off-diagonal matrix elements, giving better convergence of the series. These methods are illustrated by application to three perturbed harmonic oscillator problems--a 1-D oscillator with a linear perturbation, a 1-D oscillator with a quartic perturbation, and a perturbed 2-D oscillator, which involves degenerate states. The iterative method and the synthetic Hamiltonian method are shown to give significantly better results than the standard method.