PH-1007 (Physics)

Particle in a 1-D Box

Matter waves in an infinite square well

y(x)
U(x)
  U= U=
n=1 n=3

U = 0 for 0 < x < L

U =  everywhere else
0 L x
n=2
0 L
 Matter Waves - Quantitative
Having established that matter acts qualitatively like a wave, we want to be able to make
precise quantitative predictions about the particle (e.g. energy, momentum position etc) ,
under given conditions. Usually the conditions are specified by giving a potential energy
U(x,y,z) in which the particle is located.

Examples:
Electron in the coulomb potential produced by the nucleus
Electron in a molecule
Electron in a solid crystal
Electron in a nanostructure ‘quantum dot’
Proton in the nuclear potential inside the nucleus

U(x)
Classically, a particle in
For simplicity, the lowest energy state
consider a would sit right at the
1-dimensional
potential energy
bottom of the well. In QM
function, U(x). this is not possible.
(Why?)

x
 Classical probability distributions
Start a classical (large) object moving in a potential well (two are shown here).
At some random time later, what is the probability of finding it near position x?
Ball in a box: Ball in a valley:
U(x)   U(x)

Total energy E E
= KE + U(x) KE
E
KE
x x

P(x) P(x)

x x
Probability is equally More likely to spend time
distributed at the edges.

To predict a quantum particle’s behavior, we need an equation (i.e. Schrödinger's equation) that
tells us how the particle’s wave function, Y(x,y,z,t), changes in space and time.
 Probability distribution
Difference between classical and quantum cases
Classical Quantum
U(x) (particle with same energy U(x) (lowest energy state state)
as in qunatum case)

E E

x x
P(x) In quantum
P(x) mechanics, the
In classical
mechanics, the = y2 particle can be
particle is most most likely to be
likely to be found at the
found where its center.
speed is slowest
x x
In classical mechanics, the particle moves In quantum mechanics, the particle can also
back and forth coming to rest at each be found where it is “forbidden” in classical
“turning point” (Recall Oscillation) mechanics. We will just see, How?
 “Particle in a Box”
As a specific important example, consider a quantum particle confined to a region, 0 < x < L,
by infinite potential walls. We call this a “one-dimensional (1D) box”. This is also called “Particle in
Infinite Square Well Potential”

U(x) U = 0 for 0 < x < L

  U =  everywhere else
Quantum
dots

0 L
www.kfa-juelich.de/isi/

This is a basic problem in “Nano-science”. It’s a simplified (1D) model

of an electron confined in a quantum structure (e.g., “quantum dot”),
which scientists/engineers make

newt.phys.unsw.edu.au
 Boundary conditions
We can solve the Schrödinger Eqn wherever we know U(x). However, in
many problems, including the 1D box, U(x) has different functional forms in U(x)
 
different regions. In our box problem, there are three regions:

1: x < 0 I II III
2: 0 < x < L
yI yI
3: x > L
0 L
y(x) will have different functional forms in the different regions. U = 0 for 0 < x < L
We must make sure that y(x) satisfies the constraints (e.g., continuity) at U =  everywhere else
the boundaries between these regions.

The extra conditions that y must satisfy are called “boundary conditions”.
They appear in many problems.
 Boundary conditions  Standing waves

A standing wave is the solution for a wave confined to a region

Boundary condition: Constraints on a wave where the potential changes

Displacement = 0 for wave on string E = 0 at surface of a conductor

E=0

If both ends are constrained (e.g., for a cavity of length L), then only certain
wavelengths l are possible:
n l f
1 2L v/2L

2 L v/L
nl = 2L
3 2L/3 3v/2Ln = 1, 2, 3 …
‘mode index’

4 L/2 2v/L
L n 2L/n nv/2L
 Particle in a Box

 The waves have exactly the same form as standing waves on a string, sound waves in a
pipe, etc.

 The wavelength is determined by the condition that it fits in the box.

 On a string the wave is a displacement y(x) and the square is the intensity, etc. The
discrete set of allowed wavelengths results in a discrete set of tones that the string can
produce.


 In a quantum box, the wave is the probability amplitude y(x) and the square |y(x)|2 is the
probability of finding the electron near point x.
The discrete set of allowed wavelengths results in a discrete set of allowed energies that
the particle can have.
 Particle in a Box (1)
Regions 1 and 3 are identical, so we really only need to deal with two
distinct regions, (I) outside, and (II) inside the well
U(x)
 
Region I: When U = , what is y(x)?

d 2  ( x ) 2m I II III
2
 2 (E  U ) ( x )  0
dx 
yI yI
For U = , the SEQ can only be satisfied if: 0 L
U = 0 for 0 < x < L
yI(x) = 0 U =  everywhere else

Otherwise, the energy would have to be infinite, to cancel U.

Note: The infinite well is an idealization.

There are no infinitely high and sharp barriers.
 Particle in a Box (2) 
U(x)

Region II: When U = 0, what is y(x)?
II
d  ( x ) 2m
2

2
 2 (E  U ) ( x )  0
dx  y
d 2 (x)  2mE  0 L
2
   2 
 (x)
dx   

The general solution is a superposition of sin and cos:

2
 ( x )  A sin kx  B cos kx where, k 

Remember that k and E are related:

p 2  2k 2 h2
E   because U = 0
2m 2m 2m  2
A and B are coefficients to be determined by the boundary conditions.
 Particle in a Box (3) 
U(x)

Now, let’s worry about the boundary conditions.
I II I
Match y at the left boundary (x = 0).
yII
Region I:  I (x)  0 yI yI

0 L
Region II:  II ( x )  A sin kx  B cos kx

Recall: The wave function (x) must be continuous at all boundaries.

Therefore, at x = 0:
 I (0)   II (0)
 0  A sin 0   B cos 0 
0B because cos(0) = 1 and sin(0) = 0

This “boundary condition” requires that there be no cos(kx) term!

 Particle in a Box (4) 
U(x)

Now, match y at the right boundary (x = L).
I II I
At x = L:  I (L )   II (L )
yII
yI
 0  B sin  kL  yI

This constraint requires k to have special values: 0 L

n 2
kn  n  1, 2, ... Using k  , we find : n  2L
L 

This is the same condition we found for confined waves,

e.g., waves on a string, EM waves in a laser cavity, etc.:
n l (=
v/f) For matter waves, the wavelength is related to
4 L/2 the particle energy: E = h2/2ml2
3 2L/3
n 2h2
2 L Therefore En 
8mL2
1 2L Energy is quantized!
 The Energy is Quantized
Due to Confinement by the Potential
The discrete En are known as “energy eigenvalues”:
n l (= v/f) E
nn  2L
4 L/2
2 2 2 2
p h n h 16E1
En   
2m 2mn2 8mL2
2
3 2L/3
h 9E1
En  E1n 2 where E1 
8mL2
2 L
4E1
U= U=
1 En 2L
Important features:
E1
 Discrete energy levels. n=3
 E1  0  an example of the uncertainty principle
n=2
 Standing wave (±p for a given E)
n=1
 n = 0 is not allowed. (why?)
0 L x
 Probability and Normalization
 n 
We now know that  n ( x )  A sin  x  . How can we determine A?
 L  |y|2 Integral under
the curve = 1

We need another constraint. It is the requirement that |A|2

total probability equals 1. n=3


0 L x
The probability density at x is |y (x)|2:
  x 
2
Ptot  dx


2
 n 
L
Therefore, the total probability is the integral:

2
Ptot  A sin  x  dx
0  L 
In our square well problem, the integral is 2 L
simpler, because y = 0 for x < 0 and x > L:  A
2

Requiring that Ptot = 1 gives us: 2

A 2  n 
L Therefore,  n (x)  sin  x
L  L 
 Wave Function and Probabilities
Often what we measure in an experiment is the probability density, |(x)|2.
 n  Wavefunction =  n  Probability per
 n ( x)  A sin  x Probability amplitude
2
 n ( x)  A sin 
2 2
x unit length
 L   L  (in 1-dimension)

y |y|2
U= U=
n=1
Ground State

0 L x 0 L x

y |y|2

n=2
1 Excited State
st

0 L x 0 L x

y |y|2
n=3
2 nd
Excited State

0 L x 0 L x
 Probability Density
 n 
In the infinite well: P  x   N 2 sin.2  x (Units are m-1, in 1D)
 L 
Notation: The constant is typically written as “N”, and 2
is called the “normalization constant”. For the square well: N
L

One important difference with the classical result:

For a classical particle bouncing back and forth in a well, the probability of finding the
particle is equally likely throughout the well.
For a quantum particle in a stationary state, the probability distribution is not uniform.
There are “nodes” where the probability is zero!

|y|2
N2

n=3 0
L x
 Semiconductor Nanoparticles
(aka: Quantum Dots)

Determining QD energy
Core Shell
using the Schrödinger Equation
Core
Quantum
Dot

Red: bigger dots!

Blue: smaller dots!

Courtesy of M. Bawendi Group, Chemistry, MIT LBLUE QD LRED QD

 Particle in a Finite Well
What if the walls of our “box” aren’t infinitely high?
We will consider finite U0, with E < U0, so the particle is still trapped.

This situation introduces the very important concept of “barrier penetration”.

As before, solve the Schrödinger Eq in the three regions.

U(x)

U0
E
y
I II III

0 L
Note that the wave function is nonzero outside of the box.