We have seen that to determine the possible energies En (energy eigenvalues) which a physical system can have and the corresponding eigenfunctions (wave functions) ψn, we have to set up and solve the time-independent Schro¨dinger equation Hψn = Enψn . (8.1.1) In this equation, the wave function ψn, representing the n-th eigenstate of the system in the coordinate representation, is a function of the continuously varying eigenvalues of the position observables of the system, the number of position observables being equal to number of degrees of freedom of the system. The Hamiltonian operator H, in the coordinate representation, is a differential operator involving the continuously varying eigenvalues of the position observables and the derivatives with respect to them. Since we will be dealing with the operators mostly in the coordinate representation, we shall denote them without the caret.
We have seen that to determine the possible energies En (energy eigenvalues) which a physical system can have and the corresponding eigenfunctions (wave functions) ψn, we have to set up and solve the time-independent Schro¨dinger equation Hψn = Enψn . (8.1.1) In this equation, the wave function ψn, representing the n-th eigenstate of the system in the coordinate representation, is a function of the continuously varying eigenvalues of the position observables of the system, the number of position observables being equal to number of degrees of freedom of the system. The Hamiltonian operator H, in the coordinate representation, is a differential operator involving the continuously varying eigenvalues of the position observables and the derivatives with respect to them. Since we will be dealing with the operators mostly in the coordinate representation, we shall denote them without the caret.
Inadequate descriptions of atoms and molecules by the methods of classical physics led researchers to propose new ways to describe physical reality, giving birth to a totally new science, quantum mechanics. The methods of quantum mechanics are based on the introduction of a wave function, whose physical meaning is related to the probability of finding a certain particle, at a certain time in a volume element, positioned between x and x + dx in the x = direction, between y and y + dy in the y = direction, and between z and z + dz in the z = direction at certain time t. This wave function Ψ satisfies the Schrödinger equation, (−2mℏ2∇2+v)Ψ=EΨ,ℏ=2πh, or for short, HΨ = EΨ, where H, the Hamiltonian operator, is defined by the expression H=−2mℏ2∇2+V; h is Planck’s constant; ∇2 is the sum of the partial second derivatives with respect to x, y, and z; m is the mass of the particle; and V is the potential energy of the system. The Hamiltonian H represents the quantum equivalent of the sum of the kinetic energy and potential energy, with V being the potential energy operator and 2m−ℏ2∇2 the kinetic energy operator. Finally, E is the total energy of the system and is a number, not an operator.
Components of a field function are functions of coordinates and time and satisfy some definite differential equations, which are called field equations. Field equations can be given a very general variational or Lagrangian form, if one accepts, that a field as the dynamic system must be characterized by a definite Lagrangian function. For a mechanical system this function is written down as the sum over all the material points of the system. For a continuous system like a wave field, Lagrangian function is expressed by the space integral from Lagrangian function density: L(t) = ∫ Ld3x. (4.1) However, the variational principle deals not with the Lagrangian function but with an action S obtained from it by means of integration over x0 = ct S = c ∫ L(t)dt. (4.2) Therefore, noncovariant expression (4.1) in Lagrangian formalism is in fact intermediate and it is sufficient to consider the Lagrangian function density L, which depends on the four space-time coordinates x in an implicit way. Hereinafter, we shall simply call L by the Lagrangian. Analogously, the Hamiltonian function density H will be named the Hamiltonian. The Lagrangian depends on components of a field wavefunction ψk and on their first derivatives with respect to the space-time coordinates ∂ψk/∂x ν . In so doing we assign the meaning of generalized field coordinates to ψk, and the meaning of generalized field velocities to ∂ψk/∂x ν . The demand of lacking derivatives with respect to field functions above the first order in the Lagrangian is caused by the following reason. Dynamics of all known quantum fields is described either by equations of the first or the second order. On the one hand, these equations follow from the principle of a least action: δS = 0, (4.3) and under action variation the order of derivatives, entering L, is raised by one. The Lagrangian must be a relativistically covariant quantity, namely, a relativistic scalar L′(x′) = L(x). Thanks to the invariance under the space-time translations, we conclude that the Lagrangian must not manifestly contain any space-time coordinates x. Since dynamical observables (four-dimensional vector of the energy-momentum, the moment of momentum tensor, and so on) are real quantities, then the Lagrangian must be also a real quantity. We shall also impose the locality condition on the Lagrangian, that is, we assume that the Lagrangian depends only on the state of fields in the infinitely small vicinity of the point Particles, Fields, and Quantum x. So: L(x) = L(ψk, ∂ψk ∂xν ) = L (ψk(x), ψk;ν (x)) . General variation of an action, related with varying both field wave functions and of integration domain boundaries, is equal to: δS = δ ∫ L(x)dx = ∫ L(x′)dx′ − ∫ L(x)dx, (4.4) where dx = dx0dr. For L′(x′) we have the expression: L′(x′) = L (ψ′k(x′), ψ′k;ν(x′)) = L(x) + δL(x) = L(x) + δL(x) + dLdxλ δxλ, (4.5) In Eq. (4.5) we denote a form variation of corresponding quantities by the symbol δ. This way δL(x) represents varying the Lagrangian only on the account of the variation of field functions and field function derivatives: δL(x) = ∂L ∂ψk δψk + ∂L ∂ψk;ν δψk;ν , (4.6) and δψk(x) does a variation of a field function form: δψk(x) = ψ ′ k(x) − ψk(x).
In the previous chapter, the postulates helped us to use the wave function to find the expected results of experimental measurements by letting a dynamical quantity F (x, p, t) → F (xˆ, pˆ, t) and integrating over space. In the examples, however, the wave functions were typically given and not derived from first principles. We now endeavor to find the appropriate wave functions for a variety of physical systems in one dimension by solving the Schro¨dinger equation where for time-independent cases, the total energy is an eigenvalue. In subsequent chapters, we will extend the method to three dimensions and develop the appropriate operators, eigenvalues, and eigenfunctions for angular momentum. We will also develop methods for examining time-dependent systems. The latter chapters address special systems of interest that may be referred to as applications of quantum mechanics.
We now consider systems for which the Hamiltonian contains time-dependent interaction terms. In such cases we cannot reduce the time-dependent Schro¨dinger equation to an eigenvalue equation. However, if the time-dependent terms can be regarded as small perturbations, we can develop a form of perturbation theory that can be used to calculate the effects of time-dependent terms. Consider a system for which the Hamiltonian may be written as the sum of a dominant unperturbed part Hˆ0 and a small perturbation Hˆ ′ as Hˆ = Hˆ0 + λHˆ ′(t) , (10.1.1) where the unperturbed Hamiltonian Hˆ0 is independent of time, whereas the perturbation Hˆ ′ may depend on time. The parameter 0 < λ < 1 has been introduced to keep track of various orders of approximations as in the case of time-independent perturbation theory discussed in Chapter 8. The basic idea is that a small perturbation to the Hamiltonian will produce a small change in the wave function. For a time-dependent perturbation, this change means that a system, initially in a particular eigenstate of Hˆ0, will find itself in a time-dependent admixture of the eigenstates. Thus the time-dependent perturbation causes the system to undergo transition to different eigenstates of Hˆ0. So for time-dependent perturbations our interest lies in calculating the probabilities for transition to different states.
Throughout our discussion of the general principles of quantum mechanics we have emphasized the importance of the eigenvalues and eigenfunctions of the operators representing physical quantities. However, we have seen that solving the basic eigenvalue equations determining these is often not straightforward. In the early chapters discussing the energy eigenvalue equation (or time-independent Schro¨dinger equation) for example, we found that this could often not be solved exactly and that, even when a solution was possible, it frequently required considerable mathematical analysis. Because of this, methods have been developed to obtain approximate solutions to eigenvalue equations. One of the most important of such techniques is known as time-independent perturbation theory and will be the first method to be discussed in the present chapter. Another, known as the variational principle, will be discussed later. We shall confine our discussion to the timeindependent Schro¨dinger equation, but generalization to other eigenvalue equations is quite straightforward. We shall mainly use the wave function representation, but we shall restate some of the important results in Dirac notation so that they can be readily transformed to a matrix representation if desired.
Abstract It is a common practice to approach quantum mechanics through the study of a few, exactly soluble examples using the Schrödinger equation in position-space. The number of potential energy functions for which such closed-form solutions are available is, however, quite small. Luckily, many of them actually correspond reasonably well to actual physical systems; examples include the infinite well as a model of a free particle ina “box “ (Chapters 5 and 7), the harmonic oscillator (Chapter 9), the rigid rotator (Chapter 16), and the Coulomb potential for the hydrogen atom (Chapter