Wave functions, the Schrdinger equation, and Operators in Quantum Mechanics

A quantum mechanical particle (or system) has wave character, and is represented by a wave function

(x,y,z,t), which contains all of the information that can be known about the particle (or system). (x,y,z,t) is a solution of the quantum mechanical wave equation, the Schrdinger equation. The

Schrdinger equation is a wave equation similar to wave equations in other areas of physics, like for vibrational waves on a stretched string or electromagnetic waves. The wave equation for waves on a string can be derived from Newton's second law, F = m a. The electromagnetic wave equation is derived from Maxwell's equations. The one dimensional Schrdinger equation for a particle existing along a single space coordinate x is:

-2/2m 2 (x,t) / x2 + U(x) (x,t) = i (x,t) / t

U(x) describes the potential energy function for the particle. The wave function has the property that it is not restricted to taking on real values; it can take on complex values, by which it is meant that the function can have a real part as well as an imaginary part having the form of a real number multiplied by the imaginary unit, i, given by the square root of 1. Such a complex number can be written as c = a + i b, where a is the real part of c and b is the imaginary part of c. Such a complex number c has a complex conjugate, c*, given by a i b, with the imaginary part taking the opposite sign. A wave function solution to the Schrdinger equation can in general be any possible function of position and time. A special kind of wave function, of great importance, is one called a stationary state, which takes the mathematical form (in one dimension) of

(x,t) = (x)

e -iEt/ . In this expression, the capital psi indicates a wave function that depends on both

position and time, and the lower case psi indicates a wave function that depends only on position. The entire time dependence, for this special stationary state form, is in the exponential factor. The wave function factors into two terms, one only a function of space, the other only a function of time. The meaning of the imaginary i unit, i, in the exponent is given by the Euler relation of calculus, where e = cos() + i sin(). Why wave functions of this form are special, and why we would call them stationary states, will be made clear in a moment. The wave function solutions to the Schrdinger equation are interpreted as representing the probability that the particle could be observed at a given location and time, according to the expression:

dV
*

which gives the probability that the particle "is in" (or will be observed to exist in) the volume over which the integral is taken. The product * can be interpreted as a probability density. Notice that the product of a complex number with its complex conjugate always produces a positive, real number (work out an example with c = a + ib and c* = a ib to prove it to yourself!). This is entirely appropriate since probabilities must always be positive real numbers; there is no such thing as a negative probability, much less an imaginary or complex probability. The wave function is to be "normalized" so that if the integral is taken over all space, the result is one, i.e. there is a probability of one that the particle exists somewhere in the universe, which makes sense. This normalization condition is expressed as:

dV = 1
*

We can see that if (x,t) = (x) e -iEt/ , (taking on the special, so-called, stationary state form) then (x,t) = (x) e +iEt/ , and = e (iEt/ - iEt/ ) = e (0) = . Therefore, we see that the probability density of a wave function of this form is not a function of time. This justifies the given name of stationary state. We will see that a stationary state wave function represents a quantum mechanical particle that has definite energy, E. A quantum mechanical stationary state has a status that corresponds to the

standing wave solutions that were found to be important in classical wave mechanics. The standing wave solutions for waves on a string formed a "basis set" of independent functions that could be used to make up any other possible wave function. A wave of any arbitrary shape can be made up from a unique combination of standing waves for the system. The same relation holds in quantum mechanics, and any arbitrary quantum mechanical wave function can be made up from a unique combination of stationary state wave functions, each corresponding to some definite energy for the particle. In Quantum Mechanics, every "observable" ["o"] (knowable property of a particle or system) has a mathematical "Operator" Oo - a specific mathematical operation, or function, that can be applied to the wave function of a quantum mechanical particle such that the average value of the observable (or its statistical "expectation value") is given by the expression: The operator mathematically operates on

complex conjugate of , and the product is integrated over a volume of space. I will give some examples to clarify what this means. The simplest operator is the "Existence Operator" or "Identity Operator" OI, = 1 (just multiply by the number one). The integral is just:

yielding another function that is multiplied by , the

*

dV

dV =

(1)

dV = dV
*

which yields the probability that the particle "is in" (or will be observed to exist in) the volume over which the integral is taken. This is just the same as we discussed above, but now we see that it fits into our operator formalism. Other operators are the Energy Operator, OE, = i OPx, = - i

/ t and the (x-) Momentum Operator,

/ x . If we consider the energy operator, i

/ t, operating on a stationary state wave

function, we get i [ (x) e -iEt/ ]/ t = i (x) [ e -iEt/ ]/ t = i (x) e -iEt/ (-iE/ ) so that dV = (E) dV = E dV = E for a normalized wave function integrated over all space. This tells us that the energy of a stationary state is definite and takes on the value E. We see that the operator formalism allows us to calculate, from the wave function, the corresponding energy E of a stationary state wave function. If the wave function is not a stationary state, and corresponds to a combination of stationary state wave functions, the above calculation would yield the expectation value of the observed energy as a weighted average over the various energies of the component wave functions. We can

apply the momentum operator to the wave function for a free particle developed in lecture and in the text: Ae
i(kx- t)

where k is defined to be 2/ for the wave, and deBroglie's principle gives k=p/. Operating OPx on

, we see that -i [A e i(kx-t)]/ x = -i A e i(kx-t) (ik) = k = p so that Px dV = (p) dV = p dV = p for a normalized wave function integrated
over all space. We can begin to see why the operator - i / x is called the momentum operator; it mathematically produces the momentum as a multiplicative factor when it is used to operate on the wave function. We can now also readily see that the momentum and energy operators are hiding in plain sight in the Schrdinger equation. The right-hand side of the Schrdinger equation is just the energy operator applied to the wave function. If we replace the right-hand side energy operator with the energy E and divide everything through by the time part of the stationary state wave function we immediately get the time independent Schrdinger equation presented in the textbook. The first term of the Schrdinger equation is just the momentum operator applied twice to the wave function, and divided by (2m), so if we replace the two momentum operators with p2, and divide through by the wave function, we get the simple statement: p2/2m + U = E . We recognize p2/2m as the kinetic energy of a particle, so this is just saying that: Kinetic energy + Potential energy = Total energy. Schrdinger's equation just states the conservation of energy!