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Chemistry Education Materials Department of Chemistry

6-27-2006

The Particle in a Box (and in a Circular Box)

Carl W. David
University of Connecticut, Carl.David@uconn.edu

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Recommended Citation
David, Carl W., "The Particle in a Box (and in a Circular Box)" (2006). Chemistry Education Materials. 12.
https://opencommons.uconn.edu/chem_educ/12
 The Particle in a Box (and in a Circular Box)

C. W. David
Department of Chemistry
University of Connecticut
Storrs, Connecticut 06269-3060
(Dated: June 27, 2006)

I. SYNOPSIS and, taking the second derivative, we have

The particle in a box is the simplest problem in elemen- d2 ψ(x)

= −Aω 2 cos(ωx) − Bω 2 sin(ωx)
tary quantum mechanics, and as such is useful in more dx2
places than one can easily enumerate. For instance, the
molecular orbital theory is explained easily in terms of which is, of course,
particle in a box wavefunctions, easier than using stan-
−ω 2 ψ(x)
dard atomic orbitals. Hence, the attention to this par-
ticular problem.
This means that

h̄2
−ω 2 ψ(x) = Eψ(x)


II. INTRODUCTION −
2m
We start with a choice of coordinate systems, which, by or, said in the most straightforward manner, E is related
the way, influences the form of the solutions we are going to ω i.e.,
to get, but not the substance. Here, we choose to use
0<x<L for the region on the x-axis where the particle is 2mE
ω2 =
said to exist. for regions x<0, i.e., the negative x-axis, we h̄2
say the particle is forbidden, and mathematically, we do
this by stating that V (x) = ∞, ψ(x) = 0 in this region. . Later, we will obtain values for ω and thereby obtain
2 2 2
We say exactly the same thing in the region x>L, i.e., values of E. They will turn out to be En = n2mL h̄ π
2 , a very
the potential energy is infinite, and the wave function famous result.
vanishes. To obtain this result, we note the boundary condi-
In the domain 0<x<L, we expect the wave function tions, that the wave function vanish on the left and
to exist and have a value different from zero, but at the right boundaries. The left boundary condition, x=0 says
boundaries, we declare ψ(0) = 0, ψ(L) = 0. ψ(0) = A cos(0) + B sin(0) = A cos(0) = A i.e., A must
Then, the Schrodinger Equation (inside the domain) be chosen to be zero (as cos 0 equals 1).
becomes The right boundary condition now reads ψ(L) =
B cos(ωL) and it is a famous argument that if B is not
h̄2 2
− ∇ ψ(x) = Eψ(x) to be zero, then the cosine must. This can only occur
2m if ωhas values such that the argument ωL equates to
where m is the mass of the particle, h̄ is, of course, π, 2π, 3π, · · ·. i.e. nπ. This is the infamous quantization
Planck’s constant divided by 2π, and E is the energy, which takes place to force discrete values of E, the energy.
the eigenvalue, the allowed value of the energy that this Every text book says this better than I do, so you are re-
particle can have. We know the solution to this differ- ferred to standard texts for alternative presentations of
ential equation from elementary calculus, since there are this material.
very few functions which resurrect themselves after be- The various vave functions, now indexed with “n”, are
ing differentiated twice. One of these is the exponential, orthogonal to each other, i.e., “perpendicular” in func-
and the other is the (sine/cosine) combination (which are tion space. We see that this is just a Fourier discussion
really forms of the exponential). Assume the sines and in mufti. Thus, we have
cosines form, we have Z L

ψ(x) = A cos(ωx) + B sin(ωx) ψ1 (x)ψ2 (x)dx = 0

0

where A, B, and ω are unknown (to be determined) con- And we can change 1 to 17, and 2 to 43, and the same
stants. Taking the first derivative of this solution, we holds. Formally,
have
Z L
dψ(x) ψn (x)ψm (x)dx = 0
= −Aω sin(ωx) + Bω cos(ωx)
dx 0

Typeset by REVTEX
 2

if n6=m. Of course, when n=m, we have the normalization (a well known result).
integral The degeneracy appears when we allow the length of
the two sides of the ”box” to become equal. At that
Z L
point, we can factor the common ` = `x = `y out of this
ψn2 (x)dx 6= 0
0 formula to obtain

i.e., something other than zero. This last condition is h̄2 π 2 2

nx + n2y


Enx ,ny = 2
used to choose the (so far) arbitrary constant, A, to force 2µ`
the integral to have a value of 1, in accord with the prob-
abilistic interpretation of the wave function. Since these It is clear that the sum of two squares can add up to the
are, in the case of the particle in a box, integrals of prod- same value, e.g., 52 +22 = 22 +52 , i.e., n2x +n2y = reverse.
ucts of sines, we have We are seeing a double degeneracy emerging. (In three
dimensions, we would have a three fold degeneracy devel-
Z L 
eı
nπ
L x − e−ı
nπ
L x
2 oping, when the box became cubical.) Notice that when
A dx nx = ny , we have a loss of degeneracy.
0 2ı
q
which are trivial. A turns out to be L2 if we force the IV. A CIRCULAR BOX
integral to be 1. Again, this is explained in every text
book. Of course, the orthogonality integrals may also be Squares are nice, but we learn more from circles. Con-
evaluated using DeMoivre’s theorem. All of this turns sider a two dimensional particle in a circular box. The
out to be extraordinarily elementary. particle is restricted to be within r=R, where R is a
constant. This is a polar coordinate problem, since the
boundary condition will be that ψ(R, θ) = 0∀θ, i.e., the
III. A RECTANGULAR BOX wave function will be required to vanish at the edge of
the disk region.
When we talk about rectangular and square boxes in The first thing we have to do is transform the
two dimensional particle in a box problems, we are get- Schrödinger Equation from Cartesian to polar coordi-
ting set up to discuss degeneracy. The wave equation nates. We are going from (x, y) → (r, θ). The trans-
itself offers no hint of the complexity that is coming, but formation equations are
the boundary conditions, which are inextricably bound
to the solutions of the Schrödinger Equation, are the key x = r cos θ
here. y = r sin θ (4.1)
Assuming we are working in the x-y space (2 dimen-
sions), so ψ(x, y) is what is being sought, we have which says, given r and θ, we can compute x and y. The
reverse equations are
h̄2 ∂2ψ ∂2ψ
 
p
− + = Eψ (3.1) r = x2 + y 2
2µ ∂x2 ∂y 2 y
θ = tan−1 (4.2)
where x and y are the standard Cartesian coordinates. x
The solution to this variable separable differential equa- which says the reverse, i.e., given x and y, we can compute
tion is discussed in all texts, and has the form r and θ.
∂
nx πx ny πy First we need to express ∂x is terms of partial deriva-
X(x)Y (y) = N`x ,`y sin sin tives with respect to r and θ. From the chain rule we
`x `y
have
where nx and ny are integer quantum numbers, ranging  
∂
   
∂r ∂
   
∂θ ∂
from 1 to ∞. The box is rectangular if `x 6= `y . N`x ,`y is = +
∂x y ∂x y ∂r θ ∂x y ∂θ r
the normalization factor, which has the form
r s where we are carefully attempting to indicate what is
2 2 constant during each partial differentiation. We find that
N`x ,`y =
`x `y p !
∂ x2 + y 2
 
∂r 1 2x
Once substituted into the original Schrödinger Equa- = = = cos θ
∂x y ∂x 2 r
tion, the solution suggests that the energy is given by the y

formula: and
  2  2 !
h̄2 π 2 nx ny ∂ tan−1 y
   
∂θ x
Enx ,ny = + (3.2) =
2µ `x `y ∂x y ∂x y
 3

This latter differential is a little more difficult than the

former one was, and we attack it in a special manner,
guaranteed to bring a smile of recognition to weary read-
ers. Specifically, we use implicit differentiation. Thus dy ydx sin θ sin2 θ
d tan θ = − 2 =d = dθ + dθ
y x x cos θ cos2 θ
tan θ =
x
so which is

sin2 θ cos2 θ + sin2 θ

     
dy ydx 1
− 2 = 1+ dθ = dθ = dθ
x x cos2 θ cos2 θ cos2 θ

so, holding y constant, one has

y cos2 θ y cos2 θ
   
1 ydx dθ y 1 ydx dθ y
2
dθ = − 2 → =− 1

→ − dθ = − → =− 1

→−
cos θ x dx cos2 θ x
2 x2 cos2 θ x2 dx cos2 θ x2 x2

dθ tan θ cos2 θ so
=−
dx K      
∂ ∂ sin θ ∂
= cos θ −

dθ

tan θ cos2 θ sin θ ∂x y ∂r θ r ∂θ r
=− =−
dx y r cos θ r

Going the other way i.e., holding x constant, we have

     
∂ ∂ cos θ ∂
= sin θ +
dy dθ ∂y x ∂r θ r ∂θ r
=
x cos2 θ
The second partial derivatives then must be
so
∂ sin θ ∂




cos2 θ
 
∂θ ∂2 ∂ cos θ −
 
= ∂r θ r ∂θ r
= (4.3)
x ∂y x ∂x2 y ∂x

cos2 θ
 
∂θ
= ∂
+ ∂ cosr θ ∂




∂2 ∂ sin θ
 
r cos θ ∂y x ∂r θ ∂θ r
= (4.4)
∂y 2 x ∂y
 
cos θ ∂θ
= Equation 4.3 expands to become
r ∂y x

∂

sin θ ∂


! ∂

sin θ ∂


!
∂2 ∂ cos θ − ∂ cos θ −
 
∂r θ r ∂θ r sin θ ∂r θ r ∂θ r
= cos θ −
∂x2 y ∂r r ∂θ

i.e.,

∂2 ∂2 sin θ cos θ ∂ 2
 
sin θ cos θ ∂
= cos2 θ + −
∂x2 y ∂r 2 r 2 ∂θ r ∂r∂θ
sin2 θ ∂ sin θ cos θ ∂ 2 sin θ cos θ ∂ sin2 θ ∂ 2
+ − + + (4.5)
r ∂r r ∂r∂θ r2 ∂θ r2 ∂θ2
 4

For the y term we have

∂ cos θ ∂

! ∂ cos θ ∂

!
∂2
 
∂ sin θ ∂r + r ∂θ cos θ ∂ sin θ ∂r + r ∂θ
= sin θ + (4.6)
∂y 2 x ∂r r ∂θ

i.e.,

∂2 ∂2 sin θ cos θ ∂ 2
 
cos θ sin θ ∂
= sin2 θ − +
∂y 2 x ∂r2 r2 ∂θ r ∂r∂θ
cos2 θ ∂ cos θ sin θ ∂ 2 cos θ sin θ ∂ cos2 θ ∂ 2
+ + − + (4.7)
r ∂r r ∂r∂θ r2 ∂θ r2 ∂θ2
so, adding the two relevant results we have
z }| {
∂2 ∂2
∂2 sin θ cos θ ∂ 2
   
sin θ cos θ ∂
+ = 2+ −
∂y 2 x y ∂x2
∂r 2
| r {z ∂θ} r ∂θ∂r
z }| {
sin2 θ ∂ sin θ cos θ ∂ 2 sin θ cos θ ∂ sin2 θ ∂ 2
+ − + + 2
r ∂r r ∂r∂θ | r2{z ∂θ} r ∂θ2
z }| {
cos θ sin θ ∂ sin θ cos θ ∂ 2
− 2
+
| r {z ∂θ} r ∂r∂θ
z }| {
cos2 θ ∂ cos θ sin θ ∂ 2 cos θ sin θ ∂ cos2 θ ∂ 2
+ + − + 2 (4.8)
r ∂r r ∂r∂θ | r2{z ∂θ} r ∂θ2

which becomes where  = 2mE/h̄2 .

∂2 1 ∂ 1 ∂2 This is one of the forms of the Bessel differential equa-
2
+ + 2 2 tion. To bring it to standard form, we change variables
∂r r ∂r r ∂θ
from r to kρ = r, so
∂ρ ∂ ∂ 1 ∂
V. NOW, THE QUANTUM MECHANICS = =
∂r ∂ρ ∂r k ∂ρ
The Schrödinger Equation now becomes so, choosing

h̄2 ∂ 2 ψ 1 ∂ψ

1 ∂2ψ
 k2  = 1
− + + 2 2 + zero × ψ = Eψ
2m ∂r2 r ∂r r ∂θ we have
r
(why zero? because a particle in a box just feels its 1
boundaries, i.e., the model is of a particle free to roam k=

(linearly) until it hits a wall.) which is going to be related
to Bessel’s equation. We know this equation is variable and we have
separable, between r and θ, so we will write the solution ρ2 R00 (ρ) + ρR0 (ρ)0 + (ρ2 − m2` )R(ρ) = 0
as
It is traditional to solve this equation separately for
ψ = Rm` (r)e±me llθ different values or m, and in fact, it is rare to see solutions
which, when we substitute this into the Schrödinger for m` > 0 anywhere, since the problem, from the point
Equation, gives us of view of quantum mechanics, is quote silly.
For m` = 0 we have
h̄2 ∂ 2 Rm` (r) 1 ∂Rm` (r) m2`
 
− + − 2 Rm` (r) = ERm` (r) ρ2 R00 (ρ) + ρR0 (ρ)0 + ρ2 R(ρ) = 0
2m ∂r2 r ∂r r
which is and we start the solution by assuming an Ansatz
X
r2 R00 (r) + rR0 (r) + (r2 −
2m 2
m` )R(r) = 0 R(ρ) = ai ρi
h̄2 i=0
 5

leaving the question of the indicial equation to more ad- so

vanced study. We then have
X
R0 (ρ) = iai ρi−1
i=1

and
X
R00 (ρ) = (i)(i − 1)ai ρi−2
i=2

X
ρ2 R00 (ρ) → (i)(i − 1)ai ρi → 2a2 ρ2 + (3)(2)a3 ρ3 + (4)(3)a4 ρ4 + · · ·
i=2
X
+ρR0 (ρ)0 → iai ρi → a1 ρ + 2a2 ρ2 + 3a3 ρ3 + · · ·
i=1
X
2
+(ρ )R(ρ) → ai ρi+2 → a0 ρ2 + a1 ρ3 + a2 ρ4 + · · ·
i=0
=0

Gathering terms in the standard manner, we have ematics”, John Wiley and Sons. New York, 1962, page
548). So
a2 = −a0 /2
((3)(2) + 3)a3 = a1 R R
ρ0 = =q
a0 /2 k 1
((4)(3) + 4)a4 = −a2 = 
((4)(3) + 4)

It is fairly obvious that, contrary to other Frobenius i.e.,

Schemes in standard Quantum Chemistry, this one does  ρ 2
not lead to quantization through truncation of a power 0 2mE
==
series into a polynomial. R h̄2
Instead, this Bessel Function’s expansion never termi-
or,
nates, is never truncated, i.e., remains an infinite power
series. 2
h̄2  ρ0 2 h̄2 2.4048

The quantization occurs when the boundary condition E0 = E0 =
that the wave function vanish when we are at the rim of 2m R 2m R
the enclosure is invoked. where you have specified the value of R when setting up
The requirement that the function be zero at the the problem.
boundary (r=R), results in requiring that the Bessel The zero’s of the Bessel function act to quantize the
function have a zero, call it ρ0 . This can be found in energy via the boundary conditions, in a slightly differ-
tables of the Bessel Function.A For instance, the first ent mode than what we are used to, but never the less,
root, J0 (ρ0 ) occurs at ρ0 = 2.4048 (and 5.5207, 8.6537, we obtain a result which is quite comfortable inside the
11.7915, etc., E. Kreyszig, ”Advanced Engineering Math- context of standard quantum mechanical constructs.