In all the applications of the formalism of quantum theory, we have considered mainly time-independent potential functions, V ( r , t ) = V ( r ). Such potentials made it easier to solve exactly the Schrodinger's equation or by solving the Schrodinger's equation approximately by using perturbation theory. The solution of the Schrodinger equation for time-independent potentials is obtained by using method of separable variables. The solution of time-independent Schrodinger gives stationary states, and the time dependence of the wave function is obtained by adding a phase factor to the stationary state. The schematic that follows describes such an approach ( Figure 7.1 ).
In all the applications of the formalism of quantum theory, we have considered mainly time-independent potential functions, V ( r , t ) = V ( r ). Such potentials made it easier to solve exactly the Schrodinger's equation or by solving the Schrodinger's equation approximately by using perturbation theory. The solution of the Schrodinger equation for time-independent potentials is obtained by using method of separable variables. The solution of time-independent Schrodinger gives stationary states, and the time dependence of the wave function is obtained by adding a phase factor to the stationary state. The schematic that follows describes such an approach ( Figure 7.1 ).
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.
The previous time-dependent variation-perturbation theory, which is derived from the conventional time-dependent perturbation equations, contains two inconvenient features. When the perturbation becomes static, the wave function so obtained does not satisfy the time-dependent Schr\"odinger equation, and the perturbation equations cannot be reduced to the ordinary time-independent perturbation equations. To remove these difficulties, we introduce a perturbed time-dependent phase factor in deriving a new set of perturbation equations. We then construct the variation-perturbation functionals as in the previous theory; the perturbed wave functions are solved by minimizing these functionals. The same method is also applied to many-electron systems, using the coupled and uncoupled Hartree-Fock scheme.
There are few potentials V (r) for which the Schrödinger equation is exactly solvable. We must therefore develop approximation techniques to obtain the eigenvalues and eigenfunctions for potentials that do not lead to exactly soluble equations. One of these methods is the perturbation theory, which was developed both for time independent and time dependent phenomena. We will discuss the time independent perturbation theory. The formulation of the time independent perturbation theory is different for nondegenerate and degenerate states.
The time-dependent Schrödinger equation (TDSE) contains two variables: position and time. Therefore, the solutions are functions of both space and time (x and t, if we limit ourselves to particles moving in one dimension). It turns out that the easiest way to "solve" such an equation of two variables is to perform a separation of variables. We show that if the potential does not change with time, then certain special solutions (eigenfunctions) can be written as a product of a space function and a time function: Ψ(x,t) = ψ(x) f(t). By assuming a "separable" solution of this form, and plugging into the TDSE, the TDSE itself can be separated into two equations: the time-independent Schrödinger equation (TISE) with solution ψ(x), and the space-independent Schrödinger equation (SISE) with solution f(t). Furthermore, f(t) always equals e -iωt , while ψ(x) depends on the potential. So, for potentials that do not vary with time, we need only solve the much simpler TISE in order to investigate the energy, momentum, and so on of the particle. This is why, for the remainder of this book, we only use the TISE.
Stationary states General properties We shall consider first some general characteristics of the ‘stationary states’. These are eigenfunctions of the Hamiltonian operator: The requirement that ψ satisfies the Schrödinger equation fixes its time dependence: Notice that (4.1.2) can only be a solution if the external potential V is independent of the time: V = V ( x ). The initial function ψ 0 is not arbitrary but must satisfy the time-independent Schrödinger equation (4.1.1). Writing ψ = R e iS /ħ one thus has The following deductions may be made from (4.1.3): ( a ) The probability density is independent of the time: |ψ| 2 = R 2 0 ( X ). ( b ) The quantum potential Q = (- ħ2/2 mR 0 )∇ 2 R 0 is time-independent. Therefore so is the total effective potential: ( c ) The velocity field v = (l/ m )∇ S 0 is independent of time and hence the trajectories, found by solving m = v ( x )| x = x ( t ) , are solutions of Moreover, ψ 0 ( x ) is often a real function for many bound state problems of interest (although not for scattering states) which implies that the velocity is zero. The particle is at rest where one would classically expect it to move since the quantum force (- ∇ Q ) cancels the classical force (- ∇ K ). ( d ) The energy of all particles in the ensemble, -∂ S /∂ t , is a constant of the motion and equal to the energy eigenvalue: with (4.1.4), we have an example of the conservation of energy (cf. §3.9.3). ( e ) The total field energy is conserved: 〈Ĥ〉 = E . […]
Many physical systems cannot be solved exactly. In this case, we look for approximate methods to gain insight into their properties. Perturbation theory is one such method. When the Hamiltonian of the system doesn't change over time, one approximate method is the Time Independent Perturbation Theory, which is the subject of Chapter 10 . The infinite square well, the harmonic oscillator, and the hydrogen atom are among the few physical systems for which the Schrodinger equation can be solved exactly. For this reason, they are described in detail in most of the introductory quantum mechanics textbooks. However, most physical systems are not exactly solvable, i.e., they are described by the Schrodinger equation, whose solutions cannot be expressed in terms of commonly used functions. In order to study such systems, we try to decompose the corresponding Hamiltonian into a solvable Hamiltonian plus a small perturbation. For such cases, we say that the Hamiltonian is “close enough” to an exactly solvable Hamiltonian to warrant using perturbative methods to approximate its eigenenergies and eigenfunctions.