Some conceptual problems in 1-dimensional

Schrodinger equation

1 Particle in a box
Let us consider the situation where we have a particle in a box which is
one dimensional and has a length "a". We have aprticle enclosed in the
box which has mass m. Let us consider that the boundaries of the box are
located at x = 0 and at x = a The potential is such that it is infinity outside
the boundaries and zero inside the box so that mathematically wecan express
the potential in the form
V (x) = ∞elsewhere and
V (x) = 00 ≤ x ≤ a
Now we need to find the quantum mechanical solution to this problem. To
simplfy the situation we consider that the particle is strictly prohibited from
going outside the box,in any situation the particle will be found at different
points along the x axis inside the box only.
So
what will be the method of action to solve the problem and study
the phenomenon? We will start with 1 dimensional Schrodinger equation
of course inside the box so that our Schrodinger equation takes the form
6h2 ∂ 2 ψ(x)
− 2m ∂x2
= Eψ(x)—-(1) since the potential inside the box is zero so
the term containing potential is absent in the left hand side. Now from your
preliminary knowledge of differential equations you can figure out that the
solution is obtained by assuming a function of the form
ψ =√ Aeikx —(2) here
k = 2mE 6h
—(3)

You have to always keep in mind that the quantity K described by equa-
tion (3) is the De-Broglie wavelength of the particle. This will make it
easy to understand the physical situation. Now if we put (2) in (1) thenthe
general solution comes out as
ψ(x) = Aeikx + Be−ikx —-(4)

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A and B are constants that have to be determined.Now equation (4) is a
solution from mathematical point of view but it has to be fit enough to de-
scribe the physical situation. What I mean to say is that the solution of the
Schrodinger equation must be well behaved. To check whether our solution
is well behaved or not we will simply it and write in the form of sines and
cosines
ψ(x) = Ccos(kx) + Dsin(kx)—(5)
Now the equation (5) is simple enough but it contains a great deal of inter-
esting stuff. The important concept is that the wave function or the solution
of the Schrodinger equation is moving like a superposition of sine and co-
sine waves. Another important point is that sine and cosine functions are
different ion phase, this point will be useful in later analysis.

1.1 Boundary condition

We have mentioned that the particle is strictly to be found inside the box
and it cannot go out of the box. The particle’s inability to get out of the box
is due to the fact that the potential outside the boundaries of the box is infi-
nite. Since the particle is confined in the interior of the box so wave function
will have non zero values within the box only. Outside the box there are no
chances of finding the particle. This in turn means that the wave function ψ
is zero outside the box .
In terms of wave we can visualize a combination or superposition of sine and
cosine waves that are inside the box. so we continue with our solution (5)
ψ(x) = Ccos(kx) + Dsin(kx)—(5)

Now this solution should satisfy the physical conditions. The most impor-
tant condition is that the wave function or solution is zero outside the box.As
well behaved wave functions should be continuous so the value of ψshould be
zero at the boundary and outside . Mathematically this means
at
x = 0ψ(0) = 0 and
x = aψ(a) = 0 which implies that the above solution (5) takes theform as
shown here at x = 0 C = 0
—-(6)
so our solution takes the form
Dsin(ka) = 0—(7)
which implies ka = nπ or
k = nπa
—-(8) now equation (8) is a very simple to look at but is very cru-
cial.Equation (8) contains k in the left hand side which I told earlier is the
De-Broglie wavelength. The right hand side is a number. The quantity on

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the right hand side contains the dimension of the box. Physically this means
that the De-Broglie wavelength of the particle is related to the size of the
box by a specific relation. This required to keep the particle confined in the
box.

1.2 The quantum number "n"

The quantity "n" is an integer. Now you may ask
Why n can have integral values only? The integral values of n denote
complete waves. You can relate the phenomenon with optics where construc-
tive interference occurs for integral values only. Can n be zero? The value
of n cannot be zero as it would make the wave function zero which is
not acceptable as the particle has to be found somewhere inside the box. so
the values of n for acceptable wave function are n=1,2,3.... Thus with this
condition we have our solution wave function of the form
ψ(x) = Dsin( nπx a
)—(9)
now let us study this equation(9)

1.2.1 Particle is at one end of the box x=a

If we put x=a which is at one end of the box then
psi = 0 which means it is least likely that the particle will be found at the
ends of the box.

1.2.2 Particle is at the middle of the box

a
If we put x = then the wave function becomes
2
ψ(x) = Dsin( nπ 2
)—-(10) this gives ψ = D the sign of ndoes not cause any
physical change.
Physically this means that the maximum chance of the particle to be found
in the middle of the box.

2 Energy of the particle inside the box

Now we will find the most important quantity of the particle enclosed in a
box. The particle is moving inside the box so it has kinetic energy. However
since the potential inside the box is zero so the total energy ofthe particle is
only kinetic
1
E = mv 2 —(11)
2

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 Now we need to use some basic concepts mentioned above √
nπ 2mE
using equation (8)we have k = and equation(3) gives k = 6a
.From
a
these two equations the total energy of the particle is
2 6h2 π 2
E = n2ma ——(12)

Equation(12) is a result of fundamental importance. Let us study the key

points of the result.
(1) The energy of the particle isQuantized . This implies that the particle
can have only definite amounts of energy. The energy of this particle inside
the box depends on the quantity n or quantum number. Each value of
n corresponds to a state of fixed energy. The value n=1 corresponds to the
state of lowest energy which is called the zero point energy. It may be
noted that there is always some energy associated with the particle inside the
box.There is no concept of zero energy as n cannot take the value zero.The
lowest energy state corresponding to n=1 is called zero point energy .

(2) The case of potential in case is called as free particle. However in

case of classical physics a free particle can take any value of energy including
zero. But in the case of quantum free particle only certain definite values
of energy are possible.The quantization of energy in the case of quantum
mechanics occurs due to the fact that the particle is bound inside the box .
So we can conclude that boundary conditions give rise to quantization
ef energy .The value of zero point energy for the state n=1is given by
2 6h2
E = π2ma —-(12)

The existence of the zero point energy is a consequence of the Uncertainty

Principle. Let me explain you how this is so. If we have a particle in one
dimensional box of dimension "a" then the uncertainty in position will be
x ' a—(13) according to the uncertainty principle the momentum will be
uncertain by an amount
6h
2a
—(14). From the uncertainty principle it is not possible for a particle in
zero potential to have zero total energy as this would give ∆p = 0. So we
conclude that zero point energy is accompanied by zero point motion. This
situation is completely different from the classical case where zero energy
means no motion at all.
(3) Can we expect quantization of energy for cricket ball inside
a box of length 1meter?
No we cannot. The reason is the presence of Planck’s Constant.The small
value of Planck’s Constant makes it essential that the box and the particle
both are of atomic dimensions.

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 We have the wave function for the particle in a box given by

ψ(x) = Dsin( nπx a

)
the next question is What is D? How to evaluate the value of D?
To evaluate the value of the constant D we have to keep in consideration
that the particle will be found somewhere in the box. So if we integrate the
wave function described by the above equation over the entire dimension of
the box. The process is called normalization. In mathematical language
normalization
Ra ∗ is
0
ψ (x)ψ(x)dx = 1—(14) this yields
q
ψ(x) = a2 sin nπx a
—(15)

2.1 Sketch of the wave function of the particle inside

the box
How the wave functions look like inside the box or how can we visualize the
particle inside the box quantum mechanically is very important and interest-
ing question. To visualize the situation we first need to find the probability
density
P = ψ ∗ (x)ψ(x)—-(16) which is
P = a2 sin2 nπxa
—(17)
The probability comes out to be a constant. So we conclude that

The bound particle in the box appears as a standing wave as the

probability does not change with time
6h2 ∂ 2 ψ
The equation Eψ = − 2m ∂x2
—(16) has multiple solutions for ψ each
solution is labelled by the quantum number "n". Now we will try to see how
the things I mean the wave functions change with the value of n. This will
help us in sketching the wave functions. For each value of "n" the value of
ψ will give an eigen function and the corresponding energy will give eigen
energy.

2.1.1 n=1
our solution
q of the 1 dimensional Schrodinger equation is q
ψ(x) = a2 sin nπxa
in terms of n we can write the above equation as ψ n (x) = 2
a
sin nπx
a
—
(17)

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Wave function for n=1
q
putting n=1 in the above equation we have ψ1 (x) = a2 sin πx a
—(18)
Now equation (18) is a sine function that is
ψ1 (x) = 0f orx = 0andx = a and is maximum at the middle of the box . The
wave function will look like as shown

2.1.2 n=2
for n=2 the q wave function is
ψ2 (x) = a2 sin 2πx a
—(19) This wave function behaves as follows
x = 0ψ2 (x) = 0
x = aψ2 (x) = 0
x = a2 ψ2 (x) = 0
x = a4 ψ2 (x) = maximum

so the function will have a shape as shown

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wave function for n=2

2.1.3 wave function for n=3

The energies of the particle or any quantum mechanical system are depicted
in a diagram called energy level diagram. The corresponding probability
densities can be shown as
The particle in a box problem is also dealt as infinite asymmetric
square

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wave function for n=3

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energy level diagram

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energy level diagram

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3 What if the potential is symmetric in na-
ture? Concept of parity
We can generalize the asymmetric box in the last section . The situation can
be represented as shown in the diagram
Mathematically the potential can be expressed as follows
V (x) = +∞x < −a 2

V (x) = 0− a2 ≤ x ≤ a
2

a
V (x) = +∞x > 2

The situation is same as shifting the asymmetric potential by a2 . The sit-

uation is very interesting as it will give some new physical information. The
solution of the Schrodinger equation will be similar to the previous case so
ψ(x) = Ccos(kx) + Dsin(kx)——-(20)
k is again the De-Broglie Wavelength. The miracle will occur due to the
boundary conditions. Boundary condition requires that
ψ(± a2 ) = 0—-(21) so we have two sets of equations
now if we put x = a2 in equation (20) then we have

ψ( a2 ) = Ccos(k a2 ) + Dsin(k a2 ) = 0—-(21)

putting x = − −a 2
in equation (20)we have
ψ(− 2 ) = Ccos(k 2 ) − Dsin(k a2 ) = 0–(22) adding and subtracting (21) and
a a

(22) we have two important results

2Ccos( ka2
) = 0—(23)
ka
2Dsin( 2 ) = 0—(24)
these two equations have different solutions and hence describe different phys-
ical conditions. It is necessary that the two equations are satisfied and they
must be well behaved.
However a word of caution that needs to be mentioned is that there is no
value of k that satisfies the two equations simultaneously and we
cannot put the constants equal to zero as this will make the eigen
functions meaningless. More clearly speaking speaking let us take the
equation
Ccos( ka
2
) + Dsin( ka
2
)=0
this equation van be satisfied by two ways

eitherC = 0 or sin( ka
2
)=0

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energy level diagram

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same can be said for the other equation

either D = 0 or cos( ka
2
)=0
for the first set ψ(x) = Dsin(kx) = 0
—–(25) and for the second set
ψ(x) = Ccos(kx) = 0
—–(26)
In other words the solutions consist of two sets
(1) Cos( ka2
) = 0—-(27)
(2)sin( ka
2
) = 0—-(28)

The equations described by(27) and (28) are called transcendental equa-
tions.The solutions to these equations are simple enough it requires just to
know the high school level trigonometry.
cos( ka
2
) = 0 —(29) this equation has solutions of the form

ka
2
= π2 , 3π
2
, 5π
2
—-(30)
similarly
ka
2
= π, 2π, 3π—(31)
for the set (30) we can write a general solution oftheform
kn = nπa
–(32) where n = 1.2, 3...
–(32)
for the second set we can write the general solution as
kn = nπa
where n = 2, 4, 6..–(33)
now we need to understand the physics behind these equations. We know
that k is the De Broglie wavelength equations (32) and (33) physically show
that the De Broglie wavelength of the particle must be such that it fits inside
the box. This is required because the particle must be inside the box.

4 Parity
The equation
ψn (x) = Cn ( knax )—–(34) has the property that
ψ(−x) = ψ(x)—–(35) this type of equation is said to have even parity .
Similarly the function of the type
ψn (x) = Dsin( knax )—(36)has the property that
ψ(−x) = −ψ(x) this type function is said to have odd parity Parity defines
how the wave function changes when the origin is shifted.

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