Abstract A basic postulate of wave mechanics is that the wave function of a microscopic system develops in time according to the equation iℏ∂ψ/∂t = Hψ, where H, the Hamiltonian, is an operator which in general depends upon the time. If, and only if, the Hamiltonian is time-independent, then the solutions of this equation take the form ψ(q, t) = ∑ncnѰn(q)e-1Ent/ℏ, (2) where the individual terms Ѱn(q) are functions of the co-ordinates alone and the En are the corresponding eigenvalues of the Hamiltonian, satisfying HѰn = EnѰn. (3)
Abstract A basic postulate of wave mechanics is that the wave function of a microscopic system develops in time according to the equation iℏ∂ψ/∂t = Hψ, where H, the Hamiltonian, is an operator which in general depends upon the time. If, and only if, the Hamiltonian is time-independent, then the solutions of this equation take the form ψ(q, t) = ∑ncnѰn(q)e-1Ent/ℏ, (2) where the individual terms Ѱn(q) are functions of the co-ordinates alone and the En are the corresponding eigenvalues of the Hamiltonian, satisfying HѰn = EnѰn. (3)
We now may bring the time-dependent state functions ( )tx,Ψ into the picture, taking into account, as we already did in Eq.(29.9), that only the state function but not its position coordinate x varies with time, so that ( ) ( ) t tx dt txd ∂ Ψ∂≡Ψ ,, (30.3) Upon insertion of the expression (29.24) for the expectation value, Eq.(30.2) becomes ˆˆ ˆ ˆ ˆd d fi f i f dx i f f dx i dt dt t t t ⎛ ⎞∂Ψ ∂Ψ ∂= Ψ Ψ = Ψ +Ψ + Ψ Ψ⎜ ⎟∂ ∂ ∂⎝ ⎠∫ ∫ ∫= = = = dx∗ (30.4) On the other hand, as the Hamiltonian Hˆ is a Hermitian operator, we have ( )ˆ ˆˆ ˆ ˆˆ ˆ ˆ, f ff H i Hf f H dx i dt t ∞ ∞ ∂ ∂⎡ ⎤ + = −Ψ Ψ +Ψ Ψ + Ψ Ψ⎣ ⎦ ∂ ∂∫ ∫= = x (30.5) ( ) dx t fidxHffH Ψ∂ ∂Ψ+⎥⎦ ⎤⎢⎣ ⎡ ΨΨ+ΨΨ−= ∫∫ ∗∗ ˆˆˆˆˆ = From Eqs.(30.4) and (30.5) it follows that the evolution equation (30.2) is true only if Ψ=∂ Ψ∂ H t i ˆ= (30.6) and this is a basic result called the time-dependent Schrödinger equation. This equation describes the evolution of quantum systems in terms of time-dependent state functions that obey Eq.(30.6), but neglect the time dependence of the quantum operators. Such a description is known as the Schrödinger picture. The fifth postulate states that the timedependent Schrödinger equation must always be satisfied. Postulate 5. The evolution of the state function of a quantum system is given by the time-dependent Schrödinger equation (30.6), where Hˆ is the Hamiltonian of the system.
The basic equation of quantum mechanics is the Schrödinger equation which expresses the wave function Ψ of a quantum system as an eigenfunction of a quantized Hamiltonian operator H : HΨ = λΨ where the (real) eigenvalue λ is the quantum energy of the system in the state Ψ see equations (1.3.2), (1.3.4). Embodied already in this equation is the basic quantum mechanical principle that quantum energies cannot take on arbitrary values but are quantized : they are given by a discrete set of eigenvalues of a suitable second-order differential operator. This mathematical phenomenon of the discreteness of eigenvalues explains, for example, the observed discreteness of absorption and emission atomic spectral lines; compare remarks in Sections 1.2 and 1.3 of Chapter 1. The Schrödinger theory, and the equivalent theory of Heisenberg, Born and Jordan, represents a distinct advancement of the Bohr theory. Some early basic papers on quantum mechanics are compiled in the book [82], which includes a historic introduction by B. van der Waerden. Also see [6, 8, 9, 24, 75, 76]. These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
The postulates of quantum mechanics associate the time-evolution of a system with its time-dependent Schrödinger equation. We start by examining different solutions to this equation for a particle, represented in terms of a Gaussian wave packet, in different scenarios: free, scattered from a potential energy barrier, or trapped in a potential energy well. In some cases, we encounter stationary solutions, in which the probability density does not change in time (a standing wave). These solutions are identified as eigenfunctions of a system Hamiltonian. The properties of the Hamiltonian as a Hermitian operator are introduced, and particularly, the fact that its proper eigenfunctions can compose an orthonormal set, and that the corresponding eigenvalues are real-valued. Learning that all operators that relate to measurables are Hermitian, and that their eigenvalues relate to the measured values, we conclude that the eigenvalues of the energy operator (Hamiltonian) are the energy levels of the quantum system.
For systems which obey quantum mechanics, the formulation of the problem of treating large numbers of particles is, of course, somewhat different than it is for classical systems. The microscopic description of the system is provided by a wave function which (in the absence of spin) is a function of the classical coordinates { q i }. The mathematical model is provided by a Hamiltonian operator H which is often obtained from the corresponding classical Hamiltonian by the replacement p i → ( ħ /i)(∂/∂ q i ). In other cases the form of the Hamiltonian operator is simply postulated. The microscopic dynamics are provided by the Schrödinger equation i ħ (∂Ψ/∂ t ) = H Ψ which requires as initial condition the knowledge of the wave function Ψ({ q i }, t ) at some initial time t 0 . (Boundary conditions on Ψ({ q i }, t ) must be specified as part of the description of the model as well.) The results of experiments in quantum mechanics are characterized by operators, usually obtained, like the Hamiltonian, from their classical forms and termed observables. Operators associated with observables must be Hermitian. In general, the various operators corresponding to observables do not commute with one another. It is possible to find sets of commuting operators whose mutual eigenstates span the Hilbert space in which the wave function is confined by the Schrödinger equation and the boundary conditions. A set of such (time independent) eigenstates, termed ψ ν ( q ), is a basis for the Hilbert space.
Till 1925 the idea of what the quantum theory would be was unknown. During 1925 three different but equivalent versions of quantum theory were proposed – Schrödinger-proposed wave mechanics; Heisenberg-developed matrix mechanics and Dirac-introduced operator theory. Considering the de Broglie’s matter waves Erwin Schrödinger, an Austrian physicist, argued that if a particle like an electron behaves as a wave then the equation of wave motion could be successfully applied to it. He postulated a function varying in both space and time in a wave-like manner (hence called wave function and denoted it as ψ). This function is generally complex and assumed to contain information about a system. Schrödinger set up a linear and time-dependent wave-like equation, called Schrödinger wave equation, to describe the wave aspect of a particle taking account of de Broglie’s relation for wavelength. Physically, |ψ(X, t)|2, where ψ(X, t) is the solution of the Schrödinger equation, is interpreted as position probability density. That is, |ψ(X, t)|2 is the probability density of observing a particle at position X at time t. ψ does not give exact outcomes of observations but helps us to know all possible events and their probabilities . Further, the probability interpretation allows us to find the average or expected result of a set of measurements on a quantum system.
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.