If one assumes that the change in a ground-state wave function produced by a perturbing potential V is proportional to V, a general and very simple formula for the perturbation in energy results. The formula is illustrated with two examples.
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.
An intrinsic measure of the quality of a variational wave function is given by its overlap with the ground state of the system. We derive a general formula to compute this overlap when quantum dynamics in imaginary time is accessible. The overlap is simply related to the area under the E(tau) curve, i.e., the energy as a function of imaginary time. This has important applications to, for example, quantum Monte Carlo simulations where the overlap becomes as a simple by-product of routine simulations. As a result, we find that the practical definition of a good variational wave function for quantum Monte Carlo simulations, i.e., fast convergence to the ground state, is equivalent to a good overlap with the actual ground state of the system.
Chapter 13 is devoted to two important approximation methods used to solve time-independent problems, namely stationary perturbation theory and the variational method. Perturbation theory is developed for both non-degenerate states and degenerate states, with illustrative examples. The Stark effect is considered separately. The dielectric constant of a transparent medium as a function of frequency is shown to result from the modification of the wave function due to the perturbation of the radiation field. Two complementary topics are presented: the canonical transformation method and the Feynman-Hellman method. Finally, the possibilities of the variational method are illustrated by using it first to determine an upper bound for the energy of the stationary states of a quantum system, and then to study more complicated cases, including the partially shielded Coulomb potential produced by a neutral atom.