Particle in a Box

Chapter 3
 Translational Motion (i.e., motion through space)
We start with translational motion and the example of the particle in a
box, which is often introduced at the freshman level.

Simple model for quantum mechanics

Predicts electronic transitions of some large molecules
Application to statistical thermodynamics (See Equation 18.2 used
in Chem 222).

Later, we deal with the quantum theory of rotational and vibrational

motion.

9/13/2016 Particle in a Box 2

The three-dimensional version of the Schrodinger Equation may be written as:

h2 2 h2 2
2 + V = E ; + V = E
8 m 2m
2 2 2 2
= 2 + 2 + 2 Laplacian or "del squared"
x y z

This reduces in a 1-dimensional system to:

+ = or: + =
8 2

The first term on the left calculates the kinetic energy in 1-D.
The second term, V, calculates the potential energy, and therefore is determined
by the shape and size of the box or force field containing a particle. At first, we
set V=0.

9/13/2016 Particle in a Box 3

Particle in a 1-dimensional Square Potential Well
In the square well, the potential energy is zero by definition, except at
the walls, where it goes to infinity. Then, the Schrdinger Equation in one
dimension has the form:

h 2 d 2 ( x) h 2 d 2 ( x)
2 2
= E ( x) or: 2
= E ( x)
8 m dx 2m dx

The model is set up so that we need only consider the kinetic energy term. The
solutions would be a family of wavefunctions having the form:
Consider these as trial
= Ceikx + De ikx functions initially,
subject to refinement as
or, alternatively: different conditions are
applied.
= A sin kx + B cos kx

9/13/2016 Particle in a Box 4

Note from previous slide. If the Kinetic Energy is expressed by the
eigenvalue in the above expression:

h2k 2 p2
EK = 2 =
8 m 2m
it follows that:

2 h2k 2 hk
p = ; p=
4 2 2
This establishes a clear connection between the parameter k in the expression
eikx and the momentum of the particle.
Also, note that we find the same type of k in the expression given earlier for
the propagation of a light wave:

E ( x, t ) = E0 cos ( t kx )

9/13/2016 Particle in a Box 5

Boundary conditions.

The wavefunction must have

zero amplitude in a region of
infinite potential energy.
Therefore, the value of must
approach zero in the region of
infinite potential energy at the
walls, in order to avoid a
discontinuity in the value of .
The boundary condition implies
that should smoothly approach
zero near the walls.
= 0 at x 0 and at x L

9/13/2016 Particle in a Box 6

Figs from M&S Fig 3.2

Fig 1.9

Boundary condition for a wave on a

ring requires that the wave be
continuous.
Boundary condition for the
n = 2r particle in a box with vertical
sides (PE) is that the wave should
terminate at the ends of the box.
(See below)

9/13/2016 Particle in a Box 7

What are the acceptable solutions? Suppose we tried to use the function:

= Asin kx + B cos kx
The initial boundary condition that =0 at x=0 requires that B=0, since
cos (0) =1 - there cannot be a cosine term under these conditions.

Therefore, the acceptable solutions look like:

= A sin kx
The other boundary condition of sin kx =0 at x=L requires that:
n
kL = n ; k=
L
Also, the value of n must have the values, 1, 2, 3... This value cannot be zero,
because k must be nonzero in order for to be non-zero. This also means that
the kinetic energy and momentum must have nonzero values. Recall that k
relates to the momentum of the particle.

9/13/2016 Particle in a Box 8

 The eigenvalues for kinetic energy for the PIB are:

p 2 h2 k 2 1 h2 k 2
Ek = = 2
= 2
2m 4 2m 8 m
we can input the value of k = n/L from above to generate the result:

n2 h2
E=
8mL2
It remains to determine the value of the normalization constant, A, for the function:

= A sin kx
This requires the equation:
x=L

* 2
dx = A sin 2 kx dx = 1
x =0

Here, we have truncated the integral over all x to simply the range over which
has a nonzero value. Also, note the need to invoke the square using the
complex conjugate, since the wave function will often be a complex quantity.

9/13/2016 Particle in a Box 9

Therefore, if we set the quantity:
x= L
L

* 2
dx = A sin 2 kx dx = A2 =1
x =0
2
the value of the normalization constant, A, is seen to be:

2
A= ; we usually pick the positive value.
L
Note that the normalization constant is the same for all the PIB wavefunctions,
unlike the case of the hydrogen-atom orbitals, where the normalization
constants depend on the different quantum numbers.
In summary, the complete form of the normalized particle-in-a-box
wavefunctions is:
2 n x
n ( x) = sin (See M&S Eq. 3-27)
L L

9/13/2016 Particle in a Box 10

Orthonormality
The particle-in-a-box wavefunctions have the property that they
are individually normalized, but mutually orthogonal. In other words,
they are said to form an orthonormal set. This property is expressed by
the integral:

* m n d = mn

The quantity mn is the Kronecker Delta, which has the value 1 if m=n,
but is otherwise zero.

(See problem 3-17)

9/13/2016 Particle in a Box 11

SUMMARY

Application of the Schrdinger equation for the 1-D PIB

Wavefunctions are: 1-D Hamiltonian operator is:

2 n x
n = sin h2 d 2
L L H = 2 2
(note V=0)
8 m dx
We can simultaneously prove that this function is an eigenfunction of the KE
operator and find the KE eigenvalues using the equation:

H n = En n

h2 d 2 2 n x h 2 n 2 2 2 n x n h 2
2 2
n x
2 sin = sin = 2
sin
8 m dx 2 L L 8 2 m L2 L L 8mL L L

Therefore, we have shown that:

n2 h2
En =
8mL2
9/13/2016 Particle in a Box 12
 Properties of the Solutions of the 1-D Particle in a Box Problem
The PIB wavefunctions can also be written in complex notation as:

2 n x 1 2 ikx ikx n
n =
L
sin
L
=
2i L
( e e ) where k =
L

The terms in eikx are recognized as distinct eigenfunctions of the linear

momentum operator, as demonstrated by the following:
h d ikx
e = hkeikx = peikx Note that:
i dx

h d ikx
e = hke ikx = pe ikx
i dx
It is evident from this that the sine functions, which correspond to the energy
eigenvalues and hence individual values of k2, are also superpositions of
pairs of momentum waves having oppositely directed momentum.

9/13/2016 Particle in a Box 13

We can check that a linear combination of two momentum waves generates
eigenfunctions of the kinetic energy operator as follows:

= Ceikx + De ikx
d
= Cik eikx Dik e ikx
dx
d 2
dx 2
= Ci 2 2 ikx
k e + Di 2 2 ikx
k e = k 2
( Ce ikx
+ De ikx
) = k 2

By applying a constant multiplier, we convert this into the KE operator:

h 2 d 2 h2 k 2
2 2
= 2
8 m dx 8 m

In order to find the allowed values of k and hence momentum and kinetic
energy, we need to apply boundary conditions, as before.

9/13/2016 Particle in a Box 14

Uncertainty Principle via expectation values
We can use the information about the particle in a box to estimate the
quantities x and p in the uncertainty relationship. We use a simple
procedure from McQuarrie & Simon, Section 3.7.
Defining x and P as the standard deviations in x & p, we write for the
variances in these quantities that: We wish to calculate the
2 2 variances for x & p, and from
p = p2 p these to determine in each
2 2 case, which we take to
x = x2 x represent the uncertainty.

Distance is uncertain - the particle is "somewhere in the box"

Momentum is uncertain - a sine wave is a sum of two different momentum
waves. It is a superposition and the expectation value gives an average result.

9/13/2016 Particle in a Box 15

Eigenvalues and average or expectation values
We have seen that the operator equation related to some quantity a:
=
If we multiply on the left of each side of the equation by *,
and integrate over all space, we have:
= =

We factor out the quantity a from the integral on the right, as it relates
to something measurable, such as energy or even distance, and is a scalar
quantity. Similar factorization cannot happen on the left side of the equation, as
the quantity is an operator. This form of the equation, which is often written:

=

defines the average or expectation value of the quantity a. If a is an
eigenvalue (e.g., total energy), we have changed nothing, but if it is not well-
defined (e.g., momentum), the procedure of integrating over all space allows us
to define an average value. You may recognize the denominator as the
normalization integral, which will often have the value unity, depending on the
form of chosen.
9/13/2016 Particle in a Box 16
Section 3.8

Calculate the average value of the momentum, <p> and of the

momentum squared. <p2>.
Note that the wave functions are normalized,
(factor of 2/L takes care of both and *) so
* A that the denominator is omitted.

L L
h2 n x d n x h 2n n x n x
< p >=
i L0
sin
L dx
sin
L
dx = 2
i L 0
sin
L
cos
L dx = 0

2
h 2
L
n x d 2 n x 2h 2 n 2 2 L 2 n x
< p >= sin
2
2
sin dx = 2 sin dx
i L0 L dx L L L 0 L
2n 2 2 h 2 L n 2 2 h 2 n 2 h 2
= 3
= 2
=
L 2 L 4 L2
It makes sense that <p> = 0, because we recognize that the momentum has an
equal probability of being directed left or right.

9/13/2016 Particle in a Box 17

We could arrive at the average value of the momentum squared, <p2>,
independently, as we recognize that the eigenvalues (no averaging needed!) of
kinetic energy (p2/2m) are:
n2h2
En =
8mL2
whence we can directly evaluate <p2>:
2 2
n h
< p 2 >=
4 L2
The variance in momentum is the difference in two terms:

2 2 n2 h2
p = p2 p =
4 L2
The fact that the variance is not zero confirms that the wavefunctions for the
PIB example are not eigenfunctions of the momentum operator. That is,
momentum is not well-defined.

9/13/2016 Particle in a Box 18

Section 3.7
Let's now do the same for the variance in the position:
L L
2 n x n x 2 2 n x 2 L2 L
x = sin x sin dx = x sin dx = =
L0 L L L0 L L 4 2

The average position of the particle is in the

middle of the box no surprise there.
2
L L
2 n x 2 n x 2 n x
x 2
= sin x sin dx = x 2 sin 2 dx
L0 L L L0 L
2
L 4 n L2
2 2
L2
= 2 = 2 2
2 n 3 3 2n

Note that the mean of

x2 is less trivial, since
it depends on the
value of n.

9/13/2016 Particle in a Box 19

Therefore, the variance in x is given by:

2 L2 L2 L2 L2 L2
= x x = 2 2 = 2 2
2 2
x
3 2n 4 12 2n
L2 2 n 2
= 2 2 2
4 n 3
Now, let's calculate the quantity px, to give the Heisenberg relationship:

n2 h2 L2 2 n 2 h 2 n2
p x = 2 2 2 = 2
4 L2 4 n 3 4 3
h Note that for any allowed
p x > value of n (n1), the square
2
root is greater than unity.

This is therefore consistent with the general statement of the Heisenberg

Uncertainty Principle.

9/13/2016 Particle in a Box 20

Summary of the PIB results in one dimension

Each different
eigenvalue
corresponds to a
different quantum
number and a
different (x).

9/13/2016 Particle in a Box 21

See p. 83

In the free-electron model for butadiene, the four -electrons are placed in the two
lowest energy levels of the particle-in-a-box model. That is, the Pauli Exclusion
Principle applies. In this way, the lowest-energy electronic transition is from level
2 to level 3.

9/13/2016 Particle in a Box 22

Possibly surprisingly, the one-dimensional box provides a decent
approximation for a long-chain polyene such as -carotene. This molecule has
11 double bonds alternating with 10 single bonds. So, we have an effective box
of length ~21 times that of the average conjugated bond, let's say 0.14 nm. This
gives us a value of:
L ~ 21 x 1.4 x 10-10 m.

-carotene

Therefore, the value of h2/(8meL2) ~ 7.0 x 10-21 Joules.

9/13/2016 Particle in a Box 23

Chart showing the particle-in-a-box energy level structure for a molecule
such as -carotene

160

140

-carotene has 11 120

double bonds, and

therefore 22 electrons 100
Relative Energy

to insert into the

energy level system 80

60

40

20



0
9/13/2016 Quantum Mechanics 2 24
We have space for 2 electrons per energy level, so that the available 22 -
electrons will fill up to level n=11. The energy gap between the highest filled
energy level and the lowest unfilled energy level corresponds to the lowest-
energy electronic transition. This energy is therefore:
(122 -112) x 7.0 x 10-21 Joules = 1.60 x 10-19 Joules.
This corresponds to a wavelength ( = hc/E) of 1.24 m. This is actually about a
factor of two away from the correct number, but the calculation is very
approximate and may well have cancelling errors.

(i) The potential energy inside the box is neither zero nor constant.
(ii) Electron-electron interactions have been ignored.
(iii) Symmetry effects have not been considered.
All other factors being comparable, large molecules tend to absorb toward
longer wavelengths than smaller ones.
For several reasons, conjugated cyanine dyes show much better agreement with
PIB models than do conjugated hydrocarbons (polyenes).
9/13/2016 Particle in a Box 25
Motion in Two or more Dimensions

So far, we have dealt with the quantization of kinetic energy along a

single dimension.

The problem of a particle in a three-dimensional rectangular box is a

simple extension of the one-dimensional case. This is because the quantization
along the three dimensions can be treated separately (at least for translational
motion).

We can write the Schrdinger equation in three dimensions for the

same type of box problem with an internal potential energy of zero:

h 2 2 2 2 (3.44)
+ + = E ( x, y, z )
2 m x 2 y 2 z 2

9/13/2016 Particle in a Box 26

where 0 x a, 0 y b, 0 z c.
Note the presence of the Laplacian operator, which was introduced earlier.
The three-dimensional wavefunction satisfies the boundary conditions that it
vanishes at the walls of the box (see M&S Equation 3.46):

(0, y, z ) = (a, y, z ) = 0 for all y and z

( x, 0, z ) = ( x, b, z ) = 0 for all x and z
( x, y, 0) = ( x, y, c) = 0 for all x and y

We wish to prove that x, y and z are separate variables, which is

straightforward. Let us factor the wavefunction into three different terms:

9/13/2016 Particle in a Box 27

 ( x, y, z ) = X ( x)Y ( y ) Z ( z ) (3.47)

We substitute Equation (3.47) into Equation (3.44) and on the last line below,
divide both sides by X(x)Y(y)Z(z) as follows:

h2 2 2 2
2 ( X ( x)Y ( y ) Z ( z ) ) + 2 ( X ( x)Y ( y ) Z ( z ) ) + 2 ( X ( x)Y ( y ) Z ( z ) )
2m x y z
= E ( X ( x)Y ( y ) Z ( z ) )
h2 2 X 2Y 2Z
2 (Y ( y ) Z ( z ) ) + 2 ( X ( x) Z ( z ) ) + 2 ( X ( x)Y ( y ) )
2m x y z
= E ( X ( x)Y ( y ) Z ( z ) )
h2 1 2 X 1 2Y 1 2Z (3.48)
+ + 2
=E
2m X ( x) x 2
Y ( y ) y 2
Z ( z ) z
The last step separated the variables by dividing through by X(x)Y(y)Z(z).

9/13/2016 Particle in a Box 28

Since each term on the LHS is only a function of either x, y or z, we can evaluate
separately the Ex, Ey and Ez along each of those coordinates, and the total energy
is:

E = Ex + E y + Ez

Thus, the kinetic energy is independently quantized along the three different
coordinates, and a separate equation applies to the determination of each
component of the energy:
h2 1 2 X
2
= Ex
2m X ( x ) x
h 2 1 2Y
= Ey
2m Y ( y ) y 2 (3.50)

h2 1 2 Z
= Ez
2m Z ( z ) z 2

9/13/2016 Particle in a Box 29

This can readily rearranged into the more usual form of the Schrodinger equation:

h2 2 X
2
= Ex X ( x)
2m x
h 2 2Y
2
= E yY ( y )
2m y
h2 2 Z
2
= Ez Z ( z )
2m z
2 n x x
and there are three quantum numbers, nx, ny and nz X ( x) = sin
a a
so that the three different component wavefunctions n y y
2
appear as: Y ( y) = sin
b b
2 n z
Z ( z) = sin z
c c

9/13/2016 Particle in a Box 30

Then, the solution becomes:

8 nx x n y y nz
nx , n y , nz ( x , y , z ) = sin sin sin z
abc a b c

and the total energy (which is all kinetic) is:

nx 2 n y 2 nz 2 h 2
Enx ,ny , nz = 2 + 2 + 2 (3.57)
a b c 8m

9/13/2016 Particle in a Box 31

Degeneracy

This term means that two or more states having different

wavefunctions have the same energy.

The degeneracy can be "true" or "accidental". Cases of true degeneracy occur

in two-dimensional square and three-dimensional cubic systems simply by
permutation of the quantum numbers.

The diagram illustrates some cases where there is true degeneracy in cubic
systems (a = b = c). The values of degeneracy in such a system include 1, 3 and
6. Singly degenerate cases occur only for the situation (nx = ny = nz), whereas
if only two quantum numbers are the same, the degeneracy (g=3) and if they
are all different, there are six possibilities (g=6). (What is the first level of the 3-
D particle in a box case, for which there is an accidental degeneracy? Here, we
define this as the case where two different sets of quantum numbers result in the same
energy)

9/13/2016 Particle in a Box 32

M&S Fig 3.6

First accidental degeneracy occurs between (5,1,1) and (3,3,3)

E= 27, g=3+1=4)
9/13/2016 Particle in a Box 33
9/13/2016 Particle in a Box 34
9/13/2016 Particle in a Box 35
 0.85 nm

H2OEP

9/13/2016 Particle in a Box 36

In 2-D
EE(=n 2 2
nx ny x + ny ) in
(=nx^2+ny^2) g Total electrons
units of h2/(8mL2)
(units of h^2/(8mL^2) (degeneracy) (capacity)
1 1 2 1 2
2 1 5 2 6
For problem 3-27, the
energy levels are, after
2 2 8 1 8
conversion to cm-1,
3 1 10 2 12
E x 3000 cm-1.
3 2 13 2 16
4 1 17 2 20
3 3 18 1 22
4 2 20 2 26
4 3 25 2 30
5 1 26 2 34
5 2 29 2 38
4 4 32 1 40

A calculation in 1-D shows a monotonic increase in energy with increasing n-quantum

number (proportional to n2). The energy spacing of adjacent levels is (2n+1).
In 2-D, there are wide variations in the energy spacing, because of the addition of
squared quantities, making calculations such as 3-27 problematic.

In such cases, the problem is better handled by the particle-on-a-ring model.

9/13/2016 Particle in a Box 37

 Motion of particle on a ring:
  See problem 3-28 on p.100
Schrodinger equation: =  
8
 

Boundary condition:   = ( + 2
)

What are the allowed values of the quantum number m? We apply the
boundary condition to the wavefunction:

1
, = 
2

1
(,) =  . 
2

The expressions are equal if e2im = 1, which is true for any positive or negative
integer value of m, including zero. Thus m = 0, 1, 2.

9/13/2016 Particle in a Box 38

9/13/2016 Particle in a Box 39
Particle on a ring

In later work, we will show that confining a particle to a 2-dimensional

ring (see question 3-28) gives rise to energy levels according to:

m2h2 m2 h2
Em = 2 2
8 I 8 me r 2
Here, m is a ring quantum number, having values of m=0, 1, 2,
I is the moment of inertia ~ mer2.
Plugging in some numbers for the porphyrin ring given in problem 3-27, we find:

Em m2h 2 -1
m = = = m 1230 cm
100hc 800c 2 me r 2

If we had 18 electrons, we would populate up to m=4, so that the energy gap

would correspond to the above equation times 5242=9. The answer, on the order
of 11000 cm-1 is (surprisingly) quite close to the actual value. With this type of
crude calculation, even agreement within a factor of two is considered good.
(Note that, in Prob 3-27, the answer key used 26 electrons for some reason).

9/13/2016 Particle in a Box 40

 Details of the calculation on MathCad, for both cases for boxes of similar
dimensions ~ 1 nm

34 31
h := 6.626 10 Js me := 9.11 10 kg 2-D square box
8 1 12
c := 2.9979 10 m s L := 1000 10 m

2
h 1 5 -1
= 3.033 10 m 3033 cm-1
2 hc
8 me L

This is just the 1-dimensional base, which needs to be multiplied by the

appropriate value of nx and ny to generate the energy levels.
For a square box, these values would generate energy levels according to the
sums of the squares of two independent integers:
2, 5, 8, 10, 13, 17, 18, 20, 25, 26
all multiplied by 3033 cm-1. This uneven spacing gives large fluctuations in
calculated
9/13/2016 energy gaps. Particle in a Box 41
A further problem is presented by this square box model, since there are
degeneracies to consider.
As shown in Slide 37, the degeneracies of the levels are such that problem 3-27
with 18 -electrons would have the level (4,1; 1,4) only half filled.
The lowest-energy transition would therefore be to (3,3), which would be from
17 to 18.
On the other hand, if they allow for 22 -electrons, they would fill up to (3,3) ,
so that in that case, the transition would be from (3,3) to (4,2; 2,4), as the book
states. This difference is twice as much as the other (i.e., 2 units).
Notice that this calculation is destined to be inaccurate, independently of how
many electrons are used in the model, because of the accidental level spacings
due to differences in the sums of integers.

9/13/2016 Particle in a Box 42

 Details of the calculation on MathCad, for both cases for boxes of similar
dimensions ~ 1 nm

34 31 Ring
h := 6.626 10 Js me := 9.11 10 kg
8 1
c := 2.9979 10 m s
12
r := 500 10 m
2
h 1 5 -1
= 1.229 10 m 1230 cm-1
2 2 hc
8 me r

This again gives the fundamental formula for energy, which needs to be
multiplied by square of the appropriate quantum number for the particle on a
ring: m=0, 1, 2, or: 0, 1, 4, 9, 16, 25 multiples of 1230 cm-1. Here, the
energy gaps diverge smoothly. For example, m=0 can accommodate 2 electrons,
and thereafter 4 electrons, so that for an 18 -electron system such as a
porphyrin, we would fill up to m=4. The resulting gap between the highest
filled and lowest unoccupied level would be 9 x 1230 cm-1 = 11100 cm-1. By
comparison, a typical porphyrin absorbs in the range 14000-16000 cm-1. So, not
too bad an estimate for a very simple
9/13/2016 model.
Particle in a Box 43