Finite Square Well

Vern Lindberg

1 Solving Schroedinger’s Equation for the Finite Square Well

Consider the following piecewise continuous, finite potential energy:

U = U0 x < 0, (1)
U =0 06x6L (2)
U = U0 L < x. (3)

We want to solve Schroedinger’s Equation for this potential to get the wavefunctions and
allowed energies for E < U0 . I will refer to the three regions as regions 0, 1, and 2 with
associated wavefunctions ψ0 , ψ1 , ψ2 .

Figure 1: Finite Square Well Potential Energy

The time-invarient, non-relativistic Schroedinger’s equation is

−~2 d2 ψ
+ U ψ = Eψ (4)
2m dx2
that can be rearranged to give

d2 ψ 2m
2
= 2 (U − E)ψ (5)
dx ~

1
It is convenient to define two new variables (both positive), one for regions 0 and 2, and
one for region 1—they are wavenumbers:
2m
κ20 = (U0 − E) (6)
~2
2m
k12 = E (7)
~2
and Schroedinger’s equation becomes

d2 ψ0,2
= κ20 ψ0,2 x < 0 or L < x (8)
dx2
and
d2 ψ1
= −k12 ψ1 0<x<L (9)
dx2
In regions 0 and 2 the general solution is a linear combination of exponentials with the
same form, but with different constants, namely

ψ0 = A exp(−κ0 x) + B exp(+κ0 x) x<0 (10)

ψ2 = F exp(−κ0 x) + G exp(+κ0 x) L<x (11)

In region 1 we have the same general solution that we had for the infinite square well,

ψ1 = C sin(k1 x) + D cos(k1 x) 0<x<L (12)

Equations (10) to (12) have 7 unknowns—A, B, C, D, F, G and the energy E that is im-
plicitly contained in the variables κ0 , k1 . Therefore we need to get 7 equations to be able
to solve for the unknowns.
We will first use the requirement that the wavefunction remain finite everywhere. Consider
ψ2 as x → ∞. For this to remain finite we must require G = 0. Similarly, as x → −∞, we
require A = 0. Our solutions become

ψ0 = B exp(+κ0 x) x<0 (13)

ψ2 = F exp(−κ0 x) L<x (14)

The next step is to require that the wavefunction and its first derivative be continuous
everywhere, and in our case we look at the boundaries, x = 0 and x = L.

ψ0 (0) = ψ1 (0)
B=D (15)

2
hence ψ0 = D exp(+κ0 x).
Take derivatives of the wavefunctions,
dψ0
= κ0 D exp(κ0 x) (16)
dx
dψ1
= k1 C cos(k1 x) − k1 D sin(k1 x) (17)
dx
dψ2
= −κ0 F exp(−κ0 x) (18)
dx
and at x = 0 we get
ψ0 dψ1
(0) = (0)
dx dx
κ0 D = k1 C (19)

So
κ0
ψ1 = D sin(k1 x) + D cos(k1 x) (20)
k1
dψ1
= κ0 D cos(k1 x) − k1 D sin(k1 x) (21)
dx
There remain 3 unknowns, D, F , and E. Finding them is a bit messier! Consider the
boundary conditions at x = L,

ψ1 (L) = ψ2 (L)
κ0
D sin(k1 L) + D cos(k1 L) = F exp(−κ0 L) (22)
k1

dψ1 dψ2
(L) = (L)
dx dx
κ0 D cos(k1 L) − k1 D sin(k1 L) = −κ0 F exp(−κ0 L) (23)

We are not going much farther, but if we divided Equation (22) by Equation (23), we can
see that the constants D and F cancel leaving us with one rather ugly equation to solve for
energy E (remember this is implicitly included in the values of k1 and κ0 .) The solution
must be done numerically, and is left for other courses. At the end of this document the
next steps are shown.
How can we get the remaining constants? There is one remaining condition, normalization,
that for this problem is
Z 0 Z L Z ∞
2 2
ψ0 dx + ψ1 dx + ψ22 dx = 1 (24)
−∞ 0 L

3
Even without solving the entire problem we can make some conclusions about the wave-
function and the allowed energy levels. Recall that for an infinite square well potential of
width L the allowed energies are quantized and

~2 π 2
En∞ = n2 (25)
2mL2
with n being any positive integer. Outside the well the wavefunction is 0. We are certain
that the particle is somewhere inside the box, so ∆x∞ = L.
With the finite well, the wavefunction is not zero outside the well, so ∆xf inite > L, hence
from the uncertainty principle, ∆pfxinite < ∆p∞ x . This suggests that the average value
of momentum is less for the finite well, and therefore that the kinetic energy inside the
well is less for the finite well than for the infinite well. Indeed this is borne out with
detailed analysis. In addition, the number of allowed energy levels is finite, and there is
a possibility that a well may be sufficiently narrow or sufficiently shallow that no energy
levels are allowed.
Also note that the non-zero wavefunctions in regions 0 and 2 mean that there is a non-
zero probability of finding the particle in a region that is classically forbidden, a region
where the the total energy is less than the potential energy so that the kinetic energy is
negative. We will have more to say about this later when we discuss quantum mechanical
tunneling.

2 More of the solution

Equation(22)
Just in case you want to see more, I’ll do some. Here is Equation(23)

κ0
k1 D sin(k1 L) + D cos(k1 L) F exp(−κ0 L)
=
κ0 D cos(k1 L) − k1 D sin(k1 L) −κ0 F exp(−κ0 L)
κ0 sin(k1 L) + k1 cos(k1 L) 1
2 =
κ0 k1 cos(k1 L) − k1 sin(k1 L) −κ0
κ20 sin(k1 L) + κ0 k1 cos(k1 L) = −κ0 k1 cos(k1 L) + k12 sin(k1 L)
κ20 tan(k1 L) + κ0 k1 = −κ0 k1 + k12 tan(k1 L)
2κ0 k1 = (k12 − κ20 ) tan(k1 L) (26)

Now put in the values of κ0 and k1 from Equations (6) and (7) and do some algebra to
get r !
p 2mEL2
2 (U0 − E)E = (2E − U0 ) tan (27)
~2

4
This equation is a single equation in a single unknown, E < U0 . Once we have the details
of our particle (its mass) and the potential energy (depth U0 and width L), we can solve
it. There is no analytic solution, only a numerical one.
Consider an electron in a finite well 0.5 nm wide and 25 eV deep. Energy levels for the
finite well are compared to an equal-width infinite well in the table below. Notice that the
energies for the finite well are less than the corresponding energies for the infinite well, and
that the difference becomes greater as the energy nears the well depth. The finite well has
only 5 ”bound states.”
I had Excel so here is what I did. I made one column of energy in steps of 0.1 eV from 0.1
to 25 eV. Then I made a column for
p
2 (U0 − E)E
LHS = (28)
(2E − U0 )

and a column for r !

2mEL2
RHS = tan (29)
~2
I then made a graph of LHS and RHS on the vertical versus energy on the horizontal
and looked for intersections of the graphs. I adjused the energy at the intersection to get
something close to a perfect fit, i.e. LHS = RHS.
Energy level Infinite well (eV) Finite well (eV)
1 1.504 1.123
2 6.015 4.461
3 13.533 9.905
4 24.059 17.162
5 37.593 24.782
6 54.133 None