Wave functions

In one dimension, wave functions are often denoted by the symbol ψ(x,t).  They
are functions of the coordinate x and the time t.  But ψ(x,t) is not a real, but
a complex function, the Schrodinger equation does not have real, but complex
solutions.

The wave function of a particle, at a particular time, contains all the information
that anybody at that time can have about the particle.  But the wave function
itself has no physical interpretation.  It is not measurable.  However, the square of
the absolute value of the wave function has a physical interpretation.  In one
dimension, we interpret |ψ(x,t)|2 as a probability density, a probability per unit
length of finding the particle at a time t at position x.

The probability of finding the particle at time t in an interval ∆x about the position
x is proportional to |ψ(x,t)|2∆x.

This interpretation is possible because the square of the magnitude of a complex

number is real.  For the probability interpretation to make sense, the wave
function must satisfy certain conditions.  We should be able to find the particle
somewhere, we should only find it at one place at a particular instant, and the
total probability of finding it anywhere should be one.  This leads to the
requirements listed below.

 The wave function must be single valued and continuous. The probability of
finding the particle at time t in an interval ∆x must be some number
between 0 and 1.
 We must be able to normalize the wave function.  We must be able to
choose an arbitrary multiplicative constant in such a way, so that if we sum
up all possible values ∑|ψ(xi,t)|2∆xi  we must obtain 1.  The total probability
of finding the particle anywhere must be one.  (The area under the curve |
ψ(x,t)|2 must be 1.)

Examples:
 This is an acceptable wave function.  It is single valued and continuous.

This is an unacceptable wave function.  ψ(x,0) does not have a unique

single value at x = 0.  The wave function is not continuous.

Problem:

Consider many particles, each at t =0 described by a wave function ψ(x,0) = (2/π)

½
cos(x) for x between -π/2 and +π/2 and ψ (x, 0) = 0 for all other x.  If the position
of each particle is measured at t = 0, what is the average position of all the
particles?

Solution:
Each particle can be found in a small interval ∆x about any x between -π/2 and
+π/2 with probability (2/π) cos2(x) ∆x.  Each particle is just as likely to be found at
x > 0 than at x < 0.  The average position is x = 0.  The most likely position to find a
particle is also x = 0, because that is where the square of the wave function has its
maximum value.

Often we want to make predictions about the energy of a particle.  If we know the

eigenfunctions of the energy operator, we know the associated eigenvalues, and
therefore the possible outcomes of an energy measurement.  If a particle is
confined in some potential well, then its energy eigenfunctions resemble standing
waves in classical physics.  The energy eigenfunction ψ(x,t) for a confined particle
can be written as the product some real function ψ(x) of space and some complex
function of time.  The complex function of time just describes the oscillations in
time.
One of the simplest operations we can perform on a wave function is squaring it. 
Squaring the wave function give us probability per unit length of finding the
particle at a time t at position x.  For energy eigenfunctions this probability is
independent of time, since the square of the complex function of time is the real
number 1.  The probability of finding the particle in an interval ∆x about the
position x is equal to ψ(x)2∆x.  Energy eigenstates are therefore called stationary
states.  The probability is stationary, it does not change with time.

Energy and position are incompatible measurements.  Knowing the energy of a

particle prevents us from knowing its position and tracking it.  A stationary-state
wave function contains no information about the position of the particles as a
function of time.  All we get is probabilities.  We can certainly make a
measurement and determine the position of a particle at a particular time, but
then we lose the information about its energy.
Example 1:

An electron (m = 9.109*10-31 kg) is confined in a one-dimensional square well with

infinitely high walls and width L = 10 nm. The figure on the right shows

 (a) the lowest five energy levels En = n2π2ħ2/(2mL2), and the corresponding
energy eigenfunctions ψn(x) = (2/L) ½sin(nπx/L).  These wave functions look
like standing waves on a string. 
 (b) the corresponding probability density functions
ψn(x)2 = (2/L) sin2(nπx/L).

In the figure the wave functions and the probability density functions have an
arbitrary magnitude and are shifted by the corresponding electron energy.

Note:  The electron is not "smeared out" in the well.  We just do not have exact
position information, because energy and position are incompatible observables.

The lowest possible energy of the confined particle is its ground-state energy.  All
other possible energies are excited-state energies.  A particle can make
transitions between different energy levels when it is interacting with its
environment.  If a particle makes a transition from a lower energy level to a
higher energy level, it has to absorb an amount of energy ∆E = E high - Elow from the
outside world.  It can absorb a photon with energy hf = ∆E, or it can receive the
required energy from another particle in a collision.  If the particle makes a
transition from a higher energy level to a lower energy level, it has to release an
amount of energy ∆E = Ehigh - Elow to the outside world.  One way to do this is to
emit a photon of energy hf = ∆E.
Because the energy levels are quantized, the energies of photons involved in
transitions are quantized. The particle in the well can only interact with photons
of certain energies, it can only emit or absorb light of certain colors.

Confinement always leads to energy quantization.

Electrons in
atoms are not confined in a square well, but they are confined.  This confinement
leads to energy quantization.  If we measure the energy of an electron in an atom,
we can only measure a of a set of discrete values.  The energies of the electrons in
atoms are quantized.  Atomic spectra reveal this quantization.  Light from a hot
filament contains all the colors of the rainbow.  But light given off or absorbed by
individual atoms consists of a unique set of colors.

Example 2:

The figures on the right show the

shapes of the ground-state and excited-state wave functions of a particle trapped
in a square well with infinitely high wall and one with walls of finite height.
The wave functions in the finite well have exponentially decaying tails inside the
walls, in the "classically forbidden region".  A particle has negative kinetic energy
in this region, which classically is impossible.

In quantum mechanics the solutions in the classically

forbidden regions are exponentially decaying solutions, and they fall to zero
rapidly.  But if the region in which the kinetic energy is negative is narrow, then it
is possible for the exponential solution to smoothly connect two oscillating
solutions with positive kinetic energy on both sides of the region, and for the
particle to have a finite probability of presence in that region. This leads to the
phenomena of barrier penetration and tunneling.

The tunneling probability strongly depends on the barrier's width and height. 
Most particles approaching the barrier are reflected, but a few tunnel through the
barrier.  The probability P of finding the particle on the other side of the barrier
decreases exponentially as P = exp(-2αd), where d is the width of the barrier and
α = [(2m/ħ2 )(U - E)]½.  The tunneling probability is smaller for more massive
particles, for wider barriers, and for higher barriers (as compared to the energy of
the particle).

Problem:

A beam of electrons with kinetic energy E is incident on a potential barrier.  The

height of a potential barrier is 6 eV and the the width is 0.7 nm.  What is the
energy E of each electron if the tunneling probability or transmittance is 0.001,
i.e. if 0.1% of the electrons in the beam tunnel through the barrier?

Solution:
The tunneling probability can be expressed as
P = exp(-2αd), where α = [(2m/ħ2 )(U - E)]½ and d = 7*10-10 m.
The mass of the electron is 9.1*10-31 kg and U = 6 eV*1.6*10-19 J/eV = 9.6*10-19 J.
ln(P) = -2αd, α = -ln(0.001)/(2*7*10-10 m) = 4.93*109/m.
E = U - ħ2α2/(2m) = 9.6*10-19 J - (1.054*10-34 Js *4.93*109/m)2/(2*9.1*10-31 kg) =
8.11 x 10-19 J = 5.07 eV.
An electron with E = 5.07 eV has a probability of 0.001 or 0.1% of tunneling
through the 6 eV barrier.

Application: Tunneling Microscopy

 One can exploit tunneling to measure the
electron density on a material's surface.

The electron probability density associated with metal atoms at a surface extends
a very small distance above the surface.  When a very sharp tip is brought
sufficiently close to such a surface, there is a strong interaction between the
electrons on the surface and that of the tip, and an electric tunneling current
flows when a small voltage is applied.  At a separation of a few atomic diameters,
the tunneling current rapidly increases as the distance between the tip and the
surface decreases.  This rapid change of tunneling current with distance results in
atomic resolution, if the tip is scanned over the surface to produce an image.

Image of an actual tip.

The tip is mounted on a piezoelectric tube, which allows tiny movements by

applying a voltage at its electrodes.  Thereby, the electronics of the STM system
control the tip position in such a way that the tunneling current and, hence, the
tip-surface distance is kept constant, while at the same time scanning a small area
of the sample surface.  This movement is recorded and can be displayed as an
image of the surface topography.  Under ideal circumstances, the individual
atoms of a surface can be resolved and displayed.
This explanation is illustrated by an animated sequence.

Some STM images are shown below.

Iron atoms on a copper surface