Quantum Mechanics

Prof. P. Ramadevi
Department of Physics
Indian Institute of Technology - Bombay

Lecture – 03
Review of Particle in Box, Potential Well, Barrier, Harmonic Oscillator-I

So today what I am going to do is I am going to do a fast track on whatever you have learnt in your
first year. So that you know there is some kind of a continuity and you will appreciate further,
okay. So whoever has learnt already maybe a little bit you know repetition but it is good to go over
this repetition once so that you are all with me, okay.
(Refer Slide Time: 00:55)

So review of particle in a box, potential well, barriers, step potential, harmonic oscillator is the
theme for today. And slowly I will take you on to the delta function and some of the properties of
one dimensional problems, bounce states, scattering states.
(Refer Slide Time: 01:14)
Particle in a 1-dimensional box all of you even in the middle of a sleep, I am sure all of you know
now. Is that right? What is it? You put an infinite potential at 2 coordinates in 1-dimension at x=0
and x=L and inside the box, you treat like as if it is like a free particle. It is not exactly a free
particle because it is bound by these kinds of potential. It is constraint. So what is the wavefunction
of such a particle?

You have tried to evaluate using time independent Schrodinger equation, right. And found that the
wavefunction which satisfies the time independent Schrodinger equation, the normalised
wavefunction, is root of 2/L*Sin(n pi x/L). Everybody has derived this. I am sure you have done
it. If you have not, if you do not remember, please go back and take a look at it, okay. And the
corresponding, once I say solution to time independent Schrodinger equation, what does it mean?

You have to give both the wavefunction as well as the corresponding energy eigen values, okay.
So the En are the corresponding energy eigen values and they are also discretized, integer multiple
n squared, multiplying a common factor which is ℏ2ℼ2/2mL2, the L is the length of the box. So this
is what we mean by a solution to a time independent Schrodinger equation, okay.
(Refer Slide Time: 02:57)
For a particle in a box, you put in these condition in the derivation and then you recall this
Schrodinger equation, substitute the fact that U(x)ψ(x) is tending to infinity, right, because U is
tending to infinity. So this is something you need to worry.
(Refer Slide Time: 03:22)

So then you find the solution by setting the wavefunction to be 0 at x=0 and x=L and wavefunction
has to be continuous, right. So this is something which I said even in the last lecture that
wavefunction has to be continuous even for infinite potentials but derivative of wavefunction will
not be continuous. This is something which I stressed in the last lecture. Once you put this in, we
need the wavefunction to be only continuous, no derivative.
And inside the box, you put U=0 in the time independent Schrodinger equation. This is what I was
saying. And the most general solution is the linear combination of sin and cos. And imposing
where k is proportional to square root of the energy. And at x=0, you want your wavefunction to
vanish. And that forces you to make B to be 0. This is the way you went through the derivation.
Similarly, at x=L, you can try and show that it will be again 0 if the k is quantized in this fashion,
kL=nπ.
(Refer Slide Time: 04:54)

So once you use this, you see this one thing, when U is 0, the particle is like the free particle, right.
But if you put the free particle with some kind of a constraint, putting a constraint as potential is
infinity at x=0 and x=L, the k which would have been continuous for a free particle is no longer
continuous. It becomes discrete. The k which is given here, kL=n π where k is n π/L, that
discretization is happening because of the constraint which you have put in that the particle cannot
move beyond x=0 and x=L, okay.

This is the first feature which you see for a particle which almost looks like a free particle but not
actually. It is constraint with the potential being 0 and infinity. If it was not there, what will be the
form? k can take any value from -∞ to +∞ in continuous fashion. You agree? So this k being
discretized is because of putting this constraint that it cannot move beyond x=0 and x=L.

It has to move only between x=0 and x=L. Is that right? So discrete values start showing up if you
start putting in such kinds of bounds, infinite potential boundaries, if you start putting in, then you
start seeing that the energies are no longer continuous. It becomes discrete. So you cannot have
arbitrary energies like free particle can have from -, you know, all possible energies positive values
form 0 to infinity in continuous fashion.

Here you will have the energies to be discretized and only selective values. So these are quantum
𝑝2
features which you would not have seen in classical physics. If I give you a free particle like 2𝑚

and say that p can take -∞ to +∞ in continuous fashion. Now you cannot see it, okay. So you can
put in these quanta just like the Planck way of writing. You can define one unit of quanta to be this
𝜋 2 ℏ2
. And then you can rewrite all the allowed energies for a particle in a 1-dimensional box as
2𝑚𝐿2

𝑛2 𝐸0 .
(Refer Slide Time: 07:35)

So 𝐸𝑛 is now discretized with quanta n squared multiplying 𝐸0 . So not all energies are allowed.
Energies which are allowed are in the series. Somebody ask you whether 2𝐸0 can be found in the
spectrum? No, 3.2 𝐸0 , no and so on. So you can start saying forbidden energies are these. Such
things you cannot see in your classical system. This is why the Bohn's orbits were very specific.
You cannot go somewhere in between.

You have to be in one stationary orbit to go to the other stationary orbit and so on, okay. This
normalisation fixing depends on your domain of integration. Here the wavefunction is non-0
between 0 and L. So you need to put this normalisation condition and fix the normalisation. So
these things I am sure you have done it in your first year course.
(Refer Slide Time: 08:39)

And you have that, you have the 2 final wavefunction which I had it in my first slide as this in the
corresponding energies quantized as n squared 𝐸0 and the lowest energy is n=1 and not n=0 for
the wavefunction is 𝛹1 , n=1 is lowest energy level, corresponding energy is 𝐸1 which is equal to
𝐸0 and the wavefunction is 𝜓1 (x). And n>1 are the excited states and what is the average value
position also called expectation value?

This also we discussed last time. Formally which is 𝜓 ∗ (𝑥)𝑥 𝜓(𝑥), the operator x, 𝜓 evaluated.
These things, these integrations you can do and verify that the average value of the position is L/2
and you can also plot wavefunctions. It is the sin function, you can plot what is the expectation
value of x and so on, okay.
(Refer Slide Time: 09:43)
So far we did 1-dimensional box. You can make it into a 2-dimensional box, what is the
modification? You have x and y axis, okay. And the particle, you are taking a square box. We
could take a rectangular box also if you want but just for simplicity, let us take a square box. So
the diagram explains where the potential is infinity and inside the square box, it is 0.
(Refer Slide Time: 10:14)

So what do we have to do? You have to first write the Schrodinger equation in 2-dimension. Then
separate wavefunctions for potential energy, separable wavefunctions. If your potential energy
cannot be written as sum of a potential energy for x+ sum of potential energy for y, then separable
wavefunctions is not applicable. I am sure you know of this, right.
So separable wavefunctions, at least this particle in a 2-dimensional box falls into this class where
U (x,y) is 0 for all x and y which is less than L, right, between 0 and L if x and y are taking values,
U(x,y) is 0 and you can treat this condition being satisfied. So you can do separable wavefunction.
And then we look at the solution of particle in the 2-dimensional box.
(Refer Slide Time: 11:16)

𝜕2
So 2-dimensional Schrodinger equation is again time independent. You earlier had on a in
𝜕𝑥 2
𝜕2
particle in a 1-dimensional box. You will also have a term. So that is the first step and
𝜕𝑦 2

𝛹(𝑥, 𝑦) will be a function of both x and y. And normalisation condition will involve not just
integration over x, should also do an integration over y, right.

It is not 2-dimensional problem, straightforward extension. This is what is it? So you can put the
limits as 0 to L and 0 to L for the particle in a 2-dimensional box. If the potential energy is 𝑈2 (𝑥) +
𝑈2 (𝑦), then I can write the above equation, the top equation as an operator O which depends only
on x and another operator which depends only on y and acted on 𝜓(𝑥, 𝑦). So this is the main theme
in your differential equations.

If you can split the differential operators which depends only on x and another differential operator
which depends only on y, then what is possible? 𝜓(𝑥, 𝑦) can be written as 𝜓 of some kind of a
𝑓(𝑥) another, some other function of y, right. So that possibility exists only if you can write your
differential operator into linear sum of 2 differential operators where one is dependent on x and
another one is dependent on y.
(Refer Slide Time: 13:02)

So the 2 differential operators are these. One, 𝑂1 which is dependent on only x and 𝑂2which is
dependent on only y, differential operators, sorry this one has to be, there is a typo here, 𝑈2 should
be y, just correct it. 𝑈2 should be y, okay. For such separation of potential energy, you can write
separable functions, I am calling it as f(x) g(y).
(Refer Slide Time: 13:33)

Even though I am stressing on particle in a box, this is applicable for other situations also. This is
a formal 2-dimensional Schrodinger equation, how you can separate. If your potential energy is a
sum of, you know, different coordinates potential energies. So now you substitute it into a 2-
dimensional differential equation, Schrodinger equation and divide by f(x) g(y) and you will get
the p which is x dependent.

Put it on the left hand side. p which is y dependent, put it on the right hand side and they will be
related up to a factor of V. So this is the exact expression or equivalently this+this will be equal to
E. Because we have divided by psi, okay. Please check it. So this is just for convenience. LHS is
only dependent on x and RHS is dependent on y. And you can equate both of them to be equal to
some constant A and solve for the constant which will again become a differential 1-dimensional
differential equation.

Solve for f(x), okay. And similarly, you can solve for g(y) which will be the second 1-dimensional
differential equation. So we will now solve for the wavefunction for particle in a 2-dimensional
box.
(Refer Slide Time: 15:01)

What are the things which you see here? First thing which you will observe compared to particle
in a 1-dimensional box is that, there can be 2 different wavefunctions which can have the same
energy. So that is what is called as a degeneracy. Degeneracy will not show up in a 1-dimensional
particle in a box, okay. 1-dimensional particle in a box can also be felt as it is a bound state. It is
bound inside x=0 and x=L, okay. So this is the first thing which you will observe.
(Refer Slide Time: 15:45)

So let us solve this solution, 𝜓(𝑥, 𝑦) we are justified now that we can write f(x) g(y) even for
particle in a 2-dimensional box. And recall the wavefunction should vanish at x=L or y=L, that
you know and similarly x=0 and y=0. So put in those conditions on your wavefunction. What is
the form you will get? Inside the box, you have to solve this differential equation. This equation is
nothing.

But your a is similar to your k which we did, 𝑘 2 , no different in 1-dimensional problems, okay. So
ⅆ2 𝑓 2𝑚𝑎
is , call this as your 𝑘 2 . Here just for simplicity, we will call it as 𝑘𝑥2 if you want, okay.
ⅆ𝑥 2 ℏ2

And similarly, you have the other equation, it is not equal to a but it is E-a. Is that fine? All of you
are with me?
(Refer Slide Time: 17:13)
Okay, just to summarize, so these are the set of equations, formal operator equation is written. The
explicit form is given in the second line and then you have a formal operated equation for the y
dependence and explicit differential operator is given in the second line. What is the solution?
Very simple. I am sure all of you know the solution. You can write the first one as f(x) as A sin(
𝑘𝑥 x)+B cos (𝑘𝑥 𝑥).

2𝑚𝑎
Similarly, g(y), so you put a subscript x for the k just to keep track that is √ and 𝑘𝑦 is
ℏ2

2𝑚(𝐸−𝑎)
√ . So what is the condition? 𝑘𝑥 is this and 𝑘𝑦 is this.
ℏ2

(Refer Slide Time: 18:13)

And how do you fix the normalisation? You integrate over dx as well as dy because it is a 2-
2
dimensional problem and you can fix the normalisation. Is this correct? A prime is √𝐿 or it is going

2
to be just 2/L, has to be 2/L. For each integration, that will be a √𝐿. So this also you should correct.
And the corresponding energy for a specific wavefunction, the wavefunction here I should put an
𝑛𝑥 , 𝑛𝑦 subscript.

For that wavefunction, the corresponding energy will be 𝑛𝑥2 + 𝑛𝑦2 . (Refer Slide Time: 20:00)

Again you can define a fundamental energy unit and rewrite the particle energies in a 2-
dimensional box as 𝐸0 (𝑛𝑥2 + 𝑛𝑦2 ). This is an exercise for you. If I tell you that the energy of a
particle in a 2-dimensional box is 13𝐸0 , is the wavefunction unique? What are the possibilities?
(2, 3) and (3, 2), so the wavefunction has 𝑛𝑥 as 3 and 𝑛𝑦 as 2.

There can also be another wavefunction but 𝑛𝑥 as 2 and 𝑛𝑦 as 3. Both will share the same energy
eigen value, so that is why these 2 wavefunctions are degenerate at that level that energy level you
will say is 2 fold degenerate. Symmetry of the 2, yes. So I will give you one more thing where you
will see an accidental symmetry, one more, okay. So it happens because of the symmetry of the
square but that could also be accidental symmetry, okay. So let me try and give you that example.
(Refer Slide Time: 21:21)
50𝐸0 , what are the possibilities? There is no symmetry there. So that could also be accidental
degeneracy because the number adding as nx squared+ny squared to be some specific value, can
have so many possibilities. Case of 13𝐸0 , the symmetry of the square tells you, you can interchange
𝑛𝑥 and 𝑛𝑦 , that is what you were saying. But when you do it for 50E0, not only that symmetry but
you also have accidental things that you will have nx as 7, ny as 1, that gives you 50E0, ny as 7,
nx as 1.

You also have nx=phi and ny=phi. So it is a 3 fold degeneracy. Such possibilities also exists. So
case by case you have to find the degeneracy. It is not always 2 fold degenerate. It can be more
than that. That is all I am trying to say. So I have given you a flavour of doing it for 2-dimensional
box. It is not difficult to do a 3-dimensional box. You first put there y is a dependence on the right
hand side, x dependence on the left hand side.

Put it to be a constant. And then the y is that you separate it as y and z, go systematically, so you
will have an f of x, g of y, h of z and you can write it as a product of 3 sin functions, right. It is a
very straightforward exercise. The first, if you understand 2-dimension, you can get to. What
happens to degeneracy? The cubical symmetry will allow permutation of nx, ny, nz.
(Refer Slide Time: 23:14)
Energy will be energy Enxnynz=E0*nx squared+ny squared+nz squared, 3D box, square box or I
should technically call it as cube, okay. Is that okay? So E of nx ny nz as nx squared+ny squared+nz
squared, put a 3D square box. Can again workout degeneracies here and you can also write what
is the wavefunction x y z to be, can write it as 2/L to the power of 3/2*sin nx pi/L*sin ny pi/L, x
is there, right and then sin nz pi z/L.

Is that okay? What will be the modification if you try to put it in, kind of a cuboid with L1 L2,
length, breadth, height to be L1 L2 L3. You have to accordingly modify these things. If you do the
modification, this E0 is also cannot be written as couniversal E0, you have to appropriately put a
by L1 squared, by L2 squared, by L3 squared. You know what is that? And there is no symmetry
in that case, that can only be accidental coincidence of (()) (25:22). Is that alright, okay?
(Refer Slide Time: 25:29)
So the list which I have given is for the 2-dimensional box and then I have said for you to work it
out. There will be some assignment problems on 3D box and you can try and fix it, okay.