Quantum Book PDF

Mini book: Chapter planning1:
1. Basic concepts in Quantum Chemistry
1.1. Wave-particle duality :

In general, waves and particles are considered as two different things.
A wave is considered as a disturbance that transfers energy through
matter and space. A wave is always looked upon as an oscillation, that
can be created by applying a force in a medium. For example, when you
walk in your house, believe it or not, you create oscillations i.e. waves.
Snakes can feel these vibrations. You can also feel the vibration of your
movement if you walk on a not-so-hard surface for example how about
walking on a rope bridge, as shown in Figure ??.
Figure 1: Rope bridge
On the other hand, a particle is considered as a localized thing with

which you can associate properties like mass and volume. Localized
means having a definite boundary. In general, Waves lack these proper-
ties. We don’t really apply the concepts of mass and volume to waves.
Thus we see that waves and particles are two different things.
Figure 2: Wave and particle natures
The above clear distinction between wave and particle natures, however,
exist only for macroscopic particles. When one starts decreasing the
size of the particle the concepts of wave and particle behaviors start
mixing with each other and for very-very-small particles like electrons,
protons and neutrons the two concepts completely intermix and one
cannot really tell whether these very-very-small particles behave as wave
or as particle. In the following sections, we’ll get evidence of how, light
which is otherwise considered as a wave, can also behave as particle and
an electron, which we think as a particle can also behave as a wave.
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1.1.1. light as particle: Black-body radiation, Photo-electric effect and
Compton effect
What is light? For most of us, light is nothing but a kind of energy
or wave. Whatever we think of light, it is sure that it does not
look like a particle. So, to be on the safe side, we say light is not a
particle. When you say this you are basically supporting the con-
cept of great scholars/philosophers like Robert Hook and Christiaan
Huygens, who proposed that light is a wave. But at the same time
you are opposing great scholars/philosophers like Pierre Gassendi
and Isaac Newton who considered light as a particle. This topic
belongs to a different field – beyond the scope of this mini book –
and we don’t want to go into these details. So, let’s talk about one
of the most celebrated concept of 19th century – electromagnetic
concept of light. At the end of 19th century, to be precisely in 1865,
James Clerk Maxwell unified the ideas of electricity, magnetism and
light and came up with a new idea. He showed, through his equa-
tions, that light is an electromagnetic wave consisting of two fields
– an electric and a magnetic field – oscillating perpendicular to each
other. Light is thus an electromagnetic wave generated by the oscil-
lations of the two fields and propagates in a direction perpendicular
to the direction of the two fields. This description clearly classifies
light as a wave. Although this is one of the most celebrated concept
in physical science it is not suitable for explaining some of the ex-
perimental observations including photoelectric effect, Raman effect
and Compton effect. In fact, these experiments clearly demonstrate
that light cannot be considered as a wave rather it has corpuscular
nature.
1.1.1.1. Photo-electric effect:
As the name suggests, photo-electric effect is a phenomenon re-
lated to “photo” that means light and “electric” means electric-
ity. In fact, photo-electric effect is the ejection of electrons from
a material when the latter is exposed to a light of frequency
greater than a threshold frequency. The electrons ejected are
thus called photo-electrons and the current produced by them
is called photo-current. Let us quickly go through the charac-
teristics of photo-electric effect
Characteristics of photo-electric effect:
• Electrons are ejected out of the metal surface only when the
frequency (ν) of incident light is greater than a particular
frequency. The minimum frequency for which electrons are
ejected is called threshold frequency (ν0 ) – a characteristic
of the metal. The electrons are never ejected if ν < ν0 . The
minimum energy required to eject the photo-electrons is called
work function (W0 ).
• The kinetic energy of the photo-electrons is directly propor-
tional to frequency, ν (> ν0 ) of the incident light.
• Kinetic energy of the photo-electrons is independent of the
intensity of incident light.
• For a given frequency, ν (> ν0 ), the number of photo-electrons
ejected from the metal surface is directly proportional to the
intensity of incident light.
Now, let us try to explain these characteristics by considering
2
the wave-nature of light.
•• Intensity of light is simply the energy transfered per unit time
per unit area perpendicular to the direction of propagation of
the light. Also, the energy of a wave is directly proportional to
the square of its amplitude. Thus intensity of light is directly
proportional to the amplitude of light. Thus, in wave-picture,
a highly intense light should have high energy and hence elec-
trons can be made to eject from a metal surface by using
any highly intense light irrespective of its frequency. This is
contrary to the first characteristic mentioned above. section
•• Based on the same argument, the kinetic energy of the pho- no.
toelectrons should be proportional to the intensity of light –
contrary to the second and third characteristics above.
•• The number of photoelectrons ejected from a metal surface
and hence the photoelectric current cannot be related with
the amplitude or frequency in wave-picture of light.
Thus we see that the wave-picture of light is not able to describe
any characteristic of the photo-electric effect.
Photo-electric effect was first described successfully by Albert

Einstein, using a corpuscular picture of light. Einstein proposed
that
X light behaves as consisting of small energy packets (called pho-
ton).
X The energy of each photon of light is directly proportional to
the frequency of light. Thus,
E∝ν
(1)
=⇒ E = hν,
where h is the Planck’s constant.
X When the surface is illuminated with light, each photon is
absorbed by one electron. A part of the energy of the absorbed
photon is used by the electron to overcome the binding energy
(i.e. work function) in the atom and the remaining energy
appears as the kinetic energy of the photo-electron. According
to Principle of conservation of energy, we can write
hν = KE + W0 (2)
when ν = ν0 , KE = 0
=⇒ W0 = hν0
(3)
=⇒ KE = h(ν − ν0 )
Thus, Einstein proposed that light is no longer a continuous
thing like wave but it consist of several small particles each of
which has energy proportional to frequency of light. Now, let us
see how this particle nature of light explains the photo-electric
effect.
XX From Eqs. ?? and ??, it is obvious that when ν < ν0 ki-
netic energy becomes negative. That means no electron will
be ejected if frequency of light is less than the threshold fre-
quency. The equations has no intensity term i.e. the ejection
3
of electron does not depend upon the intensity of light. [Char-
acteristic 1]
XX Kinetic energy is proportional to the frequency and is inde-
pendent of intensity of light, as evident from Eq. ?? [Charac-
teristics 2 and 3]
XX In this particle-picture of light, intensity is simply number of
photons emitted per unit time per unit area perpendicular
to the direction of propagation of light. That means, larger
the intensity larger will be the number of photons and hence
larger will be the number of electrons emitted. Thus, for a
given frequency (> ν0 ) the number of electron emitted and
hence the amount of photoelectric current is proportional to
the intensity of light. [Characteristic 4]
Thus, we see that photoelectric effect can be described only if
we consider light as a particle and not as wave. This is a clear
evidence that light is indeed a particle. Now, we’ll go for another
evidence – Compton effect.
1.1.1.2. Compton effect [1923]:
Compton effect is the increase in wavelength (equivalently, de-
crease in frequency) of an x-ray when it is scattered by an
electron. The amount by which wavelength increases is called
Compton shift. Arthur H. Compton, while studying the in-
teraction of x-ray with matter noticed that after scattering the
wavelength of the scattered x-ray beam is larger than that of the
incident x-ray beam. If one consider light (here, x-ray) as wave
then this increase in wavelength is unexpected. Why? Well,
since the energy of wave is proportional to the intensity and
independent of the frequency (or wavelength), after scattering
(i.e. after exchanging energy with the electron) the intensity
only should decrease and frequency (or wavelength) should re-
main intact. Thus, this observation also demonstrate a case
where wave-picture of light is inadequate. Compton explained
this observation by considering the particle-nature of light. If
one considers the particle nature of light – as considered in case
of photo-electric effect – one can easily realize that after inter-
action with the electron a part of energy (which is proportional
to the frequency of light) is absorbed by the electron and hence
the energy of the scattered photon becomes less than that of
the incident photon and hence the scattered photon should have
smaller frequency (larger wavelength) than the incident photon.
Now, let us move to do some mathematics related to Compton
effect and derive the expression for compton shift.
Derviation of compton shift:
Thus these two experiments/observations clearly demonstrate

that light is not a continuous thing and it has a particle nature.
1.1.2. de Broglie hypothesis [1924]

Based on the above observations and particularly influenced by the
idea of Einstein that light has particle-like nature, Louis de Broglie,
in 1924, in his PhD thesis, proposed that electrons and all matter
also have wave-like properties. This is called wave-particle duality.
4
At that time, it was just a hypothesis but later on, in 1927, it was
verified by Davisson and Germer in the famous double-slit experi-
ment. According to de Broglie, the wavelength of a particle of mass
m, moving with velocity v is given by
h
λ= , (4)
mv
where h is the Planck’s constant. There are several interesting things
to note.
• The wave associated with a material particle is called matter-
wave.
• The wavelength of a matter-wave decreases with the increase in
mass or velocity of the associated particle.
• Since the value of h is very small (order of 10−34 in SI unit),
wave-nature becomes significant only for a particle of very small
mass and small velocity.
• For a daily-life particles (dust particle, sand grains, car, human
beings etc), wave-like character is negligible and hence does not
affect their behavior significantly. However, it does not mean
that these things don’t have wave-like properties.
• For sub-atomic particles like electrons, protons, and neutrons,
wave character is significant and it affects their behavior, which
can be observed in different experiments.
• If a sub-atomic particle moves at a very high speed, it loses its
wave-nature to some extent.
• It is very obvious that if a wave moves in a circle then the wave
will survive only when the perimeter (circumference) of the circle
equals an integer number of wavelengths i.e. 2πr = nλ, r being
the radius of the circle. Otherwise, the wave will just disappear
because of destructive interference [Fig. ??].
Figure 3: Wave on a circle
If we assume the wave to be a matter wave then we can use

Eq. ?? here, which gives
nh
2πr =
mv (5)
nh
=⇒ mvr =
2π
This is nothing but the Bohr’s postulate of stationary orbits.
Thus, Bohr’s stationary orbit is a consequence of de Broglie’s
wave-particle duality.
1.1.3. Electron as wave [1927]
As we have seen above, light, which is not associated with any
mass or volume i.e. particle-like properties, indeed has a parti-
cle nature. Now, we will see that electron, which has a definite
5
mass and volume, can also behave as a wave (as proposed by de
Broglie). This can be demonstrated by the famous double-slit ex-
periment. Surprisingly, the same experiment can be used to demon-
strate that light behaves as a wave rather than a particle. So,
double-slit experiment is really an amazing piece of work in sci-
ence (It is not included in your chemistry syllabus.). You can watch
this beautiful illustrative youtube-video on double-slit experiment
(https://tinyurl.com/y8xsam6p).
1.2. Concept of operators:
Let us consider some simple mathematical equations.
• 1+2=3
• 3×2=6
d 2
• dx x = 2x
What are those symbols (+, ×) in the first two equations and what is
d
that dx ? You never thought about this. Am I right? OK, the sym-
d
bols (+, ×) and dx are nothing but representation of some mathematical
operation. I know, you knew this. But do you know, these are called
mathematical operators or simply operators. Thus, an operator is noth-
ing but a symbol representing some mathematical operations. In other
words, operators are short-hand notation of some mathematical rules.
For example, whenever we see the symbol + between two numbers or
two variables, it says that the two numbers or the two variable should
be added together obeying the mathematical rules of addition. Simi-
d
larly, when we see the symbol dx preceding something, it says that we
should take a derivative of that something with respect to the variable
x, following the rules of differentiation.
1.2.1. Eigenfunctions, eigenvalues,
X Some operators after operating on a function return another
d 2 d
function. For example, dx x = 2x. Here, the operator dx oper-
2
ates on function x and returns a different function x.
X It is also possible that an operator after operating on a func-
tion returns the same function multiplied by a constant. For
d 5x
example, dx e = 5ex . In this case, the function is called an
eigenfunction of the operator and the constant is called eigen-
value of the function.
d2 2
X Similarly, dx 2 (sink1 x + cosk1 x) = −k1 (sink1 x + cosk1 x). Thus,
d2 2
(sink1 x+cosk1 x) is an eigenfunction of the operator dx 2 and −k1
is the corresponding eigenvalue.

X But what does eigenfunctions and eigenvalues really mean? Later
on, in this quantum chemistry course, you’ll come to know that
operators basically represent some properties of the system and
the functions represent some states of the systems. The eigen-
functions represent those states of the system in which the sys-
tem can reside under certain conditions and when the system is
in that state the value of the property (corresponding to that
operator) will be equal to the eigenvalue. I hope this is quite
confusing!! Am I right? OK, read it again, this time slowly and
let me know if it makes sense.
X Another attempt to understand the meaning of eigenfunction
and eigenvalue. Let us suppose two conditions – (a) when you
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are relaxing and (b) when you are jogging. Now, suppose there
is an instrument that displays ”jogging” only when your heart
beat is above 110 per minute. But when it is less than 110 beats
per minute, it does not display anything. So,it is obvious that
the instrument will give a display only when you are jogging.
Thus, here your two conditions are two states. Your ”jogging”
condition is an eigenfunction of the instrument (the operator)
and the display is the eigenvalue.
1.2.2. Linear operators:
Suppose, f and g are two functions, k is a constant and Â is an
operator. Now, if
Âkf = k Âf, Operator does not operate on a constant.

(6)
Â(f + g) = Âf + Âg distributive property
then the operator Â is called a linear operator.

1.2.3. Hermitian operator
• An operator is said to be Hermitian if it satisfies the following
rule, called turn-over rule
Z Z
∗ ∗ ∗
f Âgdτ = Â f gdτ, (7)
where ∗ represents complex conjugate. Such operators are also

called self-adjoint operator.
• What is the meaning of self-adjoint? Adjoint is a terminology
used (in this context) for a particular transposition of a matrix.
When you transpose a matrix and takes complex conjugate of
each element then the resultant matrix is called adjoint of the
original matrix. For example, let a matrix

A11 A12
A=
A21 A22
The adjoint of this matrix will be
∗
A11 A∗22

†
A =
A∗12 A∗22
Thus, if
1 + 2i 2 + 3i
A=
4 − 5i 5 + 7i
then
† 1 − 2i 4 + 5i
A =
2 − 3i 5 − 7i
• Thus, a Hermitian matrix is one for which A = A† . A real
symmetric matrix will always be Hermitian. For example
 
1 2 3
A= 2  5 7 = A†
3 7 9
is a Hermitian matrix.
7
• Ok, the concept of hermitian or hermiticity is very much clear
in the context of matrix. But how can we understand it in the
context of operators?
• Actually, later on, you’ll came to know that operators can be
represented by a matrix and then Hermitian operators are al-
ways represented by real symmetric matrices.
• According to above definition of Hermitian operator,
Z Z
∗ ∗ ∗
f Âgdτ = Â f gdτ
Here, you can consider R the left hand side as Af g element of the
∗
matrix A i.e. Af g = f Âgdτ . Similarly, the element Agf will
be given by, Agf = g ∗ Âf dτ . By definition, Agf is the transpose
R
of Af g . Now, if you take the complex
conjugate
of Agf then it
becomes A∗gf = g Â∗ f ∗ dτ = Â∗ f ∗ gdτ =right hand side.
R R
But, taking transpose followed by complex conjugation is the

operation of making adjoint. Thus, right hand side of the above
equation is an adjoint of the left hand side. Hence, the hermitian
operator (or matrix) A is self-adjoint.
• Now, you know, what is hermitian operator and why it is called
self-adjoint? Let us now have a look at some important charac-
teristics of a hermitian operator.
Characteristics of a hermitian operator
X The eigenfunctions of a hermitian operator can be complex or
real but the eigenvalues are always real.
Proof: Let Â be a hermitian operator and f and a are the
eigenfunction and eigenvalue respectively. Then
Âf = af
Multiplying both sides (from left) by f ∗ and integrating the

resultant, we can write
Z Z
f Âf dτ = a f ∗ f dτ
∗
(8)
Now, taking adjoint of the above equation, we get

Z ∗ Z
∗
Âf f dτ = a f ∗ f dτ (9)
R ∗
∗
R
By definition, f Âf dτ = Âf f dτ (as Â is hermitian.).
Thus,
Z Z
a f ∗ f dτ = a∗ f ∗ f dτ
Z (10)
∗ ∗
(a − a ) f f dτ = 0.
Since f ∗ f dτ 6= 0, this means a − a∗ = 0 =⇒ a = a∗ , which

R
is possible only when a is real. Thus, the eigenvalue(s) of a
hermitian operator are always real.
8
X Two eigenfunctions of a hermitian operator are always orthog-
onal to each other.
Proof: Let f and g be two different eigenfunctions of a hermi-
tian operator Â and the corresponding eigenvalues be a and b
respectively. Thus
Âf = af, Âg = bg
From definition of hermitian operator, we can write
Z Z ∗
f ∗ Âgdτ = Âf gdτ
Z Z
f ∗ bgdτ = (af )∗ gdτ
Z Z (11)
b f ∗ gdτ = a f ∗ gdτ, since a is real, a∗ = a
Z
(b − a) f ∗ gdτ = 0.
R ∗ f and g are two different functions, b 6= a. This means,

Since,
f gdτ = 0. Thus, two different eigenfunctions of a hermitian
operators are always orthogonal to each other.
X Hermitian operators are represented by a real symmetric matrix.
X The eigenfunctions of a hermitian operator form a ‘complete
set’. That means, any arbitrary function can be expressed as a
linear combination of eigenfunctions of hermitian operator.
X Any observable (e.g. energy, momentum) is always represented
by a hermitian operator.
1.2.4. Orthogonality and normalization of function
Normalization and orthogonality are two important concepts arise
when we deal with eigenfunctions in quantum mechanics.
• A function f is said to be normalized if
Z
f ∗ f dτ = 1
• If a function is square integrable i.e if for a function (f ),

Z
f ∗ f dτ = finite
over a space then it will be possible to normalize that function.

• The meaning of normalization and more will be discussed later
on.
• Two functions f (x) and g(x) are said to be orthogonal to each
other if they satisfy the relation
Z
f ∗ (x)g(x)dτ = 0 (12)
• Orthogonality of two functions simply means that the two func-

tions do not share a common space in the given interval (i.e. in
the limit of the integration).
• That means, if we plot the two functions in the same range of
the variable x then the overlap between the graphs of the two
functions will be zero.
9
• More about orthogonality will be discussed later on.
1.2.5. Commutation of operators
X What to do when two operator appear as a product? Let us
consider Â and B̂ are two operators and f be a function. Then
ÂB̂f means that at first B̂ should operate on f and then on the
d √
result of B̂f , Â should operate. For example, if Â = dx , B̂ = 2
(i.e. square root operator) and f = x2 + 2x + 1. In this case,
h i
ÂB̂f = Â B̂f
d hp 2
2
i
= x + 2x + 1 at first, B̂ operates on f
dx (13)
d
= [± (x + 1)] On result of B̂f, Â will work
dx
= ±1
and
h i
B̂ Âf = B̂ Âf
r
2 d 2 (14)
= (x + 2x + 1) at first, Â operates on f
p dx
= 2 2(x + 1) B̂ will work on the result of Âf .
X The above example reflects a very important characteristic about

the product of two operators. As we see above, the result of
d √
operation of the product of dx and 2 operators on the same
function depends upon the order of operations. This usually
happens i.e. ÂB̂f 6= B̂ Âf .
X However, for some pair of operators, result of operations of the
products of the two operators may not depend upon the order
of operations i.e. ÂB̂f = B̂ Âf . In such cases, the two operators
are said to commute with each other.
X Let Â = k1 x and B̂ = kx2 , that means operator Â represents a
multiplication by k1 x and operator B̂ represents multiplication
by kx2 , k1 and k2 being constants. Now, if the function f = g(x),
then
k2
ÂB̂f = k1 x × × g(x) = k1 k2 g(x) (15)
x
and
k2
B̂ Âf =× k1 x × g(x) = k1 k2 g(x) (16)
x
Thus, the operators k1 x and kx2 commute with each other.
h i
X The quantity Â, B̂ = ÂB̂ − B̂ Â is called commutator of the
h i
two operators. when Â, B̂ = 0, the two operators commute
h i
and when Â, B̂ 6= 0, the two operators do not commute.
h i
X The quantity Â, B̂ = ÂB̂ + B̂ Â is called anti-commutator of
+
the two operators.
X So, now you know what a commutator is. But what does it
really mean, when we say that two operators commute with each
10
other? If you go to the literal meaning of commute with each
other, you will be surprised. It means, the two operators can
commute – talk – or interact – with each other. It means, some
sort of communication is possible between the two operators.
But what kind of communication can be possible between two
operators?
X The answer is eigenfunctions. When two operators commute,
they share the same set of eigenfunctions. That means, when
two operators commute, both of them can extract information
from a set of functions.
X In other words, when two operators commute, an eigenfunction
of one operator will also be an eigenfunction of the second oper-
ator and when the system is in such a state, both the properties
– corresponding to the two operators – can be measured simul-
taneously and with any degree of precision. This is related to
Heisenberg Uncertainty principle and will be discussed in more
details there. For now, you should know that if two operators
do not commute then you cannot measure the two properties
simultaneously with any arbitrary degree of precision.
X This also means that when two operates commute that means
informations about the system i.e. about the states of the sys-
tem can transfer through these operators.
X This can also be put as when two operators commute that means
the information about the system is not lost when the observ-
ables corresponding to these operators are measured.
X Or like, two commuting operators behave as a transparent medium
for the passage of information about the system and hence in-
formation is not lost during their measurement.
1.2.6. Fundamental commutator: Some of the fundamental commutation
relationships in quantum mechanics are as follows
• [x̂, ŷ] = [x̂, ẑ] = [ŷ, ẑ] = 0, where x̂, ŷ and ẑ are the position
operators in three Cartesian coordinates directions.
Proof: Position operators are simply multiplication by the co-
ordinates (x, y or z). Thus, if f be a function then
[x̂, ŷ] f = x̂ŷf − ŷx̂f = xyf − yxf = 0, x and y are numbers
[x̂, ẑ] = [ŷ, ẑ] = 0 can similarly be proved.

• [p̂x , p̂y ] = [p̂x , p̂z ] = [p̂y , p̂z ] = 0, where p̂x , p̂y and p̂z are the
three Cartesian components of linear momentum operator, re-
spectively.
Proof: Linear momentum operator (e.g. in x−direction) is
given as
d
p̂x = −i~ ,
dx
√ h
where i = −1 andh ~ = 2π . Let a function f = f (x, y). Then,
[p̂x , p̂y ] f (x, y) = p̂x p̂y f (x, y) − p̂y p̂x f (x, y)

d d d d
= −~2 f (x, y) + ~2 f (x, y)
dx dy dy dx (17)
2 2

d d
= −~2 f (x, y) − f (x, y)
dxdy dydx
11
Note that f (x, y) is a state function. So, the term in parenthesis
will vanish. Hence [p̂x , p̂y ] = 0. Similarly, other commutators
can be proved.
• [ŷ, p̂x ] = 0.
Proof: Let f (x, y) be the function. Therefore,
[ŷ, p̂x ] f (x, y) = ŷ p̂x f (x, y) − p̂x ŷf (x, y)
df (x, y) d
= −i~y + i~ {yf (x, y)}
dx dx (18)
df (x, y) df (x, y)
= −i~y + i~y
dx dx
=0
• [x̂, p̂x ] = i~.
Proof: Let f (x) be the function.
[x̂, p̂x ] f (x) = x̂p̂x f (x) − p̂x x̂f (x)
d d
= −i~x f (x) + i~ {xf (x)}
dx dx (19)
df (x) df (x)
= −i~x + i~x + i~f (x)
dx dx
= i~f (x)
Thus, [x̂, p̂x ] = i~
h i
• L̂x , L̂y = i~L̂z , where L̂x , L̂y and L̂z are the three Cartesian
components of angular momentum.
Proof: The x, y and z-component of angular momentum oper-
ator is given by
L̂x = ŷ p̂z − ẑ p̂y
L̂y = ẑ p̂x − x̂p̂z (20)
L̂z = x̂p̂y − ŷ p̂x
If f be the function, then
h i
L̂x , L̂y f = L̂x L̂y f − L̂y L̂x f
= (ŷ p̂z − ẑ p̂y ) (ẑ p̂x − x̂p̂z ) f − (ẑ p̂x − x̂p̂z ) (ŷ p̂z − ẑ p̂y ) f

d d
= −~ 2
y −z (zfx0 − xfz0 )
dz dy

d d
yfz0 − zfy0

− z −x
dx dz

d d d d
= −~2 y (zfx0 ) − y (xfz0 ) − z (zfx0 ) + z (xfz0 )
dz dz dy dy

d d d d
− z (yfz0 ) + z zfy0 + x (yfz0 ) − x zfy0

dx dx dz dz
00 0 00 00
= −~2 z 2f

yzf xz + yfx − yxf zz −

xy
00 00 2 0 00 00 0

+ zy −
zxf zyf
zx + z f + xyf − xzf − xf

yx zz yz y
2
0 0

= −~ yfx − xfy
= i~ [−ŷ p̂x + x̂p̂y ] f
= i~L̂z f
(21)
12
h i
Thus, L̂x , L̂y = i~L̂z
h i
• L̂x , ŷ = i~z.
Proof: Let f be a function.
h i
L̂x , ŷ f = L̂x ŷf − ŷ L̂x f
= (ŷ p̂z − ẑ p̂y ) yf − y (ŷ p̂z − ẑ p̂y ) f

d d d d
= −i~y + i~z yf − y −i~y + i~z f
dz dy dz dy

d(yf ) d(yf ) 2 0 0
= i~ −y +z + y fz − yzfy
dz dy

2 0 0 0
2 0
= i~ − y fz − 0 + zyf y + zf + y fz − yzf

y

= i~zf
(22)
h i
Thus, L̂x , ŷ = i~z
1.3. Uncertainty relation:
X Suppose, you want to determine the position of a particle. This is
quite simple, you simply fix the origin of the coordinate system and
with respect to that origin you can determine the position of the
particle.
X Suppose, you also want to measure velocity of the particle, which is
now moving. This time the position of the particle will vary with
time.
X If the particle does not move with very hight velocity, it will be
possible to tell both the position and velocity of the particle simul-
taneously to a very high degree of precision.
X But, what if the particle is moving with a very hight velocity? In
this situation there will be some uncertainty in determining both
the position and velocity simultaneously.
X Now, if the particle is a sub-atomic particle (or in general, say, a
quantum particle) then you cannot determine both the position and
velocity of the particle simultaneously to any arbitrary degrees of
precision.
X The reason is, because, as mentioned before, a quantum system does section
not precisely behave as a material particle – it has both particle as no.
well as wave-like characters – you cannot determine the position of
a wave (or could you!!).
X This failure of measuring both the position and velocity (and hence
momentum) of quantum systems simultaneously is a fundamental
limit posed by the nature and was first put in the form of a principle
by Werner Heisenberg in 1927. This is called Heisenberg uncertainty
principle.
X It states “It is impossible to determine both the exact position and
exact momentum of a quantum system, at the same time, not even
theoretically.”
X If the uncertainty in determining the position of a quantum system
is ∆x and uncertainty in determining its momentum is ∆px then
13
the product of the two uncertainties will always be greater than or
at least equal to ~/2 i.e.
~
∆x∆px ≥ (23)
2
X You may notice that the product of the two uncertainties is of the
order of Planck’s constant, which is 10−34 in SI unit. This is an
extremely small quantity.
X So, how much important is this uncertainty principle? Let’s have a
quick look in two cases – (1) a quantum particle e.g. electron and
(2) a macroscopic particle e.g. a bicycle.
Importance of uncertainty principle:
XX Let, an electron is moving with velocity 2.2 × 106 m per sec (This is
approximate speed of an electron in Hydrogen atom) and the uncer-
tainty in determining the velocity be 10%. This means uncertainty
in velocity is ∆v = 2.2 × 105 m per sec. We know, the mass of elec-
tron is 9.31 × 10−31 kg. This gives, the uncertainty in momentum
as ∆p = m∆v = 9.31 × 10−31 × 2.2 × 105 = 2.0482 × 10−25 kg.m /
sec. Using Eq. ??, the uncertainty in position of the electron will be
≥ 6.626 × 10−34 /(4.0 × 3.14 × 2.0482 × 10−25 ) = 0.2075 × 10−9 m =
0.2075 nm. Remember, the dimension of an atom is 0.1–0.5nm.
Thus, if the velocity of the electron will be determined with a cer-
tainty of 90% (i.e. 10% uncertainty) then the position of the elec-
tron determined simultaneously will be of the dimension of size of
the atom i.e. the determined position will be highly uncertain. In
fact, regarding the position you can just say that the electron is in
the atom.’
XX Now, let us take the example of a bicycle. Let the mass of the
bicycle be 8 kg and is moving with a velocity of 18 km/h (5 m/sec).
Let the uncertainty in determining the velocity be 10% (same as we
considered for the electron). This gives, ∆p = m∆v = 8×5×0.10 =
4 kg.m/sec. And hence ∆x ≥ 6.626 × 10−34 /(4.0 × 3.14 × 4) =
0.1318 × 10−31 m. This is an extremely small value and is absolutely
negligible in comparison to the dimension of the bicycle. Thus if the
velocity (or momentum) determined for the bike is 90% accurate
then the position will be 100% accurate. That means both position
and momentum of the bike can be determined simultaneously.
XX Thus, we see that a small uncertainty in velocity can lead to very
large degree of uncertainty in the position of a en electron (a quan-
tum system), whereas in case of a bicycle (a macroscopic system)
the same amount of uncertainty in velocity leads to practically no
uncertainty in position. This demonstrates that uncertainty princi-
ple is extremely significant for quantum systems.
More about uncertainty relationship:
• So, Heisenberg uncertainty principle tells about the natural limit of
simultaneous determination of position and momentum (or velocity)
only. Why only position and momentum?
• Is the principle also valid for other pairs of observables?
• If yes, then what special characteristics do these observables possess
to fit into uncertainty relationship?
To answer these questions, we’ll have to go back a little bit.
14
- As mentioned previouslysection no.), in quantum mechanics, ob- (
servables are represented by mathematical operators.
- Some pair of operators commute with each other and some don’t.
- If you remember, the two operators corresponding to position, x̂ and
momentum p̂x do not commute with each other. Such pair of ob-
servables (operators), which do not commute are called canonically
conjugate variables.
- The uncertainty relationship holds only for those who do not com-
mute i.e. canonically conjugate variables.
Applications of Heisenberg uncertainty principle:
• Non-existence of free electron in nucleus of an atom
– This is an interesting example. Through this, we’ll prove that
an electron does not exist in nucleus of an atom.
– But before that let me tell why we are interested in this topic.
– You know that radioactive nucleus emits three types of radi-
ations α, β and γ. Among these three, β radiation consist of
electrons.
– Thus, it is really surprising that electrons come out of the nu-
cleus. Does that mean nucleus of an atom contains electrons?
In order to prove that electrons do not exist in nucleus, we proceed
as follows.
# The maximum kinetic energy of an electron emitted out of the
nucleus (as β radiation) is 4MeV.
# The rest mass of an electron is m0 = 9.1 × 10−31 kg.
# The diameter of a nucleus is ≈ 2 × 10−14 m.
# If the electron exists in nucleus and if one determines the posi-
tion of electron then the maximum uncertainty in determining
the position of the electron would be ∆x = 2 × 10−14 m.
# Thus, the minimum uncertainty in momentum would be
~
∆p( min) =
2∆x
6.626 × 10−34 J. sec
=
4.0 × π × 2 × 10−14 m
= 0.2638 × 10−20 kg. m. sec−1
# Thus, if the electron exists in nucleus, it will have a minimum
momentum of pmin = 0.2638 × 10−20 kg. m. sec−1
# Hence, the minimum energy of the electron would be
2
Emin = p2 c2 + m20 c4
2 2 4
= 0.2638 × 10−20 × 3 × 108 + 9.1 × 10−31 3 × 108
= 0.62631 × 10−24 + 0.0067076 × 10−24
= 0.633 × 10−24
Emin = 0.7956 × 10−12 J, [1 eV = 1.6 × 10−19 J]
Emin = 0.4973 × 107 eV
Emin = 4.973 MeV
# Thus, we see that if the electron has to stay in the nucleus, it’s
energy would be greater than the maximum energy observed.
Hence, electrons cannot exist in the nucleus of an atom.
15
• Size of H-atom
• Energy of a harmonic oscillator
• Energy of particle in a box from Heisenberg uncertainty principle
(This will be discussed when we study the particle in a box problem
– sec 1.5)
1.4. Basic Postulates of quantum mechanics (This was actually a topic on
Schödinger time-independent equation but I changed it for convenience.)
Just like, the behavior of macroscopic particles is governed by some
fundamental equations such as Newton’s laws of motion, the behav-
ior of quantum mechanical systems can also be studied using a fun-
damental equation called Schrödinger’s equation. But before exploring
Schrödinger’s equation let us discuss the basic postulates of quantum
mechanics i.e. those things which are pre-assumed for developing the
theory of quantum mechanics. The basic postulates of quantum me-
chanics and a brief discussion of each are as follows
Postulate 1. The state of a quantum mechanical system is completely described
by a mathematical function, Ψ(r, t), called wavefunction.
Discussion on postulate 1:
– The wavefunction is nothing but a mathematical function. If
you think, you can realize that this is a very simple concept.
Suppose, a circle – a very simple thing. All the properties of a
circle can be described by a simple equation and that is
x2 + y 2 − r2 = 0 (24)
How did we reach at this equation? Simply by combining all

the information about a circle. For example, a circle is a two-
dimensional symmetrical object. The circle has a boundary that
is defined at equal distance from the origin. Thus, the shape of
a circle depends upon two Cartesian coordinates x and y (two-
dimensional). The size of the circle is related to one variable
– its radius. Thus, an equation that can describe everything
about a circle should contain three things – the two Cartesian
coordinates and the radius – related in such a way that the
boundary of the circle lies at equal distance from the origin.
Eq. ?? has all these information and hence we can say that the
wavefunction for a circle is Ψcircle = x2 + y 2 − r2
– It is obvious that the wavefunction should depend on the co-
ordinates of each entity in the system. The state of a system
can change with time, if a force is applied on it and hence the
wavefunction should depend on time also. Thus, wavefunction
is a function of {r} (coordinates of all the entities in the system)
and t (time).
– The equation x2 + y 2 − r3 = 0 also depends upon x, y and r but
it is not an acceptable equation for a circle. Similarly, just any
function cannot be accepted as a wavefunction. For a function
to be a valid wavefunction, it should satisfy certain conditions.
– A valid wavefunction is a single valued, continuous and quadrat-
ically integrable function.
– All the partial first derivatives of a valid wavefunction with re-
spect to the coordinates of each entity in the system should also
be continuous.
16
– A valid wavefunction should satisfy the boundary conditions for
the system.
– A valid wavefunction should be finite everywhere within the
boundary of the system.
Postulate 2. An observable (e.g. energy) is represented by a linear hermitian
operator.
– Why should an observable be represented by an operator? – To
determine the value of an observable one must perform some sort
of activity/experiment involving the system and that’s what an
operator does. An operate operates on a function and gives a
result.
– Suppose you want to determine the taste of a mango then you
should eat (= activity/experiment) a mango. If you eat a ba-
nana, you can not determine the taste of a mango.
– Similarly, if you operate an operator on a non-eigenfunction then
you cannot get the property represented by that operator. Thus,
the value of an observable is obtained only by operating the
corresponding operator on an eigenfunction.
– Why should the operator representing an observable should be
hermitian? It’s simple. An observable is something, which is
real and a real result is always obtained when the operator is
hermitian. So the operator representing an observable should
be hermitian. A non-hermitian operator does not represent an
observable.
Postulate 3. The wavefunction (Ψ) of a system evolves with time following the
equation
dΨ
ĤΨ = i~ , (25)
dt
where Ĥ is the Hamiltonian or total energy operator of the system.
– When a system, in a particular state, be acted upon by a time-
varying force (field), the system may switch from one state to
another. This equation (Eq.??) represents that time evolution
of the state of the system.
– This is the time-dependent Schrödinger equation. One can easily
extract the time-independent Schrödinger equation from it.
– Note that there is only one Schrödinger equation – The time-
dependent one. Time-independent form is simply derived from
the time-dependent ones (We’ll do it at some point.).
– Now, let us talk a little bit about Hamiltonian i.e. Ĥ. As
mentioned above, it is the total energy operator. section
– What does mean by ”Total energy operator”? It means it rep- no.
resents the total energy of the state of the system on which it
is operating.
– A system can have two types of energy – Kinetic and potential.
– Apart from these two, a system can also have an energy due to
interaction with the external applied field e.g. interaction with
and external electric field or magnetic field.
– Thus, Ĥ can be written as
Ĥ = T̂ + V̂configuration + V̂interaction , (26)
17
where T̂ is the kinetic energy operator, V̂configuration is the poten-
tial energy operator due to the relative position of the particled
in the system and V̂interaction is the potential energy operator due
to the interaction of the system with the external applied field.
– Later on, we’ll discuss more about these operators in particular,
how do they look like?
Postulate 4. In an experiment, measuring an observable (corresponding to the
operator Â) of the system, the only value that can be obtained will
be the eigenvalue (a) that satisfies the equation, ÂΨ = aΨ, where
Ψ is the wavefunction of the system in that state.
– As discussed previously, we know that when an operator oper- section
ates on a function, the result can be another function (different no.
from the original one) or the same function.
– In an experiment (applying an operator), the system (wavefunc-
tion) does not change (you don’t end up with a banana while
determining the color of a mango!!). This clearly says that the
wavefunction should be an eigenfunction of the operator. And
if that is the case then the observable will simply be the eigen-
value.
– You can say that the state of a system changes when a time-
varying field (time-dependent operator) is applied. Exactly.
You are right. But, then we are talking about the time-evolution
of state of the system and the properties calculated in that case
is not the property of a particular state of the system rather in
this case the property is a transition property. That means a
property related to the transition of the system from one state
to another. This can be explained by giving example of light ab-
sorption, for example. So, above, when we say observable that
means the property of a particular state of the system.
Postulate 5. The average value of an observable, corresponding to the operator
Â, for a system in state Ψ is given by
+∞
Ψ∗ ÂΨdτ
R
−∞
hAi = +∞
(27)
R
Ψ∗ Ψdτ
−∞
Before discussing this postulate, let us first get rid of the denomina-
tor in Eq. ??. We can do this by considering that the wavefunction
+∞
R ∗
Ψ is normalized and hence Ψ Ψdτ = 1. This reduces Eq. ?? to
−∞
Z+∞
hAi = Ψ∗ ÂΨdτ (28)
−∞
– This postulate basically reflects the statistical nature of quan-
tum mechanics.
– It actually differentiates two different cases
18
– (1) If a system is in a pure quantum state Ψ and if Ψ is an eigen-
function of the operator Â then it is sure that a measurement
of property A will always gives the eigenvalue a. If we repeat
the measurement then also each time we get the value a. This
is quite obvious!! Isn’t it?? Let go for the second case.
– (2) If a system is in a mixed state. Mixed state simply means
when the wavefunction of the system is a linear combination
of several states. Let the system be in a mixed state of two
states φ1 and φ2 and the total wavefunction of the system be
Ψ = c1 φ1 + c2 φ2 . In this case, if we measure the property A
then we can get the two different eigenvalues (corresponding
to the functions φ1 and φ2 . Both of these functions are eigen-
functions of Â, otherwise the total wavefunction will not be an
eigenfunction of this operator). The probability of obtaining the
eigenvalue corresponding to φ1 will be c21 and that correspond-
ing to φ2 will be c22 . Since the total probability of obtaining the
eigenvalue should be 1 (a measurement always leads a result),
c21 + c22 = 1.
Postulate 6. The wavefunction of the system is antisymmetric with respect to the
interchange of coordinates between any two fermions in the system.
– Suppose a system consist of two particles 1 and 2 having coordi-
nates x1 and x2 respectively. Let, Ψ(x1 , x2 ) be the wavefunction
of the system. On exchanging the coordinates of the particles
i.e. particle 2 be placed to x1 and particle 1 be placed to x2
then the resultant wavefunction will be Ψ(x2 , x1 ). Then, the
postulate simply says Ψ(x1 , x2 ) = −Ψ(x2 , x1 )
– This is a basic criteria for fermions and comes from Fermi-Dirac
statistics.
– Fermions are entities having half-integral spin. For example,
electrons, protons and neutrons have a spin = 1/2 and hence
are fermions.
– Fermions obeys Pauli exclusion principle i.e. two fermions can
not reside in the same quantum state in a system.
1.4.1. Kinetic and potential energy operators in Hamiltonian
• In Eq. ??, we encounter the Hamiltonian, which is a total energy
operator.
• We have also seen that Ĥ consists of kinetic energy operator T̂
and potential energy operators V̂configuraiton and V̂interaction .
• Let us discuss each of these operators in details. This is impor-
tant because in next sections we’ll have to deal with Hamiltonian
explicitly.
• Kinetic energy operator:
– To derive the expression of kinetic energy operator, we’ll start
with the expression for the linear momentum operator. For
convenience let’s first consider a one-dimensional case i.e.
d
p̂x = −i~
dx
– Kinetic energy of a system is related to the linear momentum
19
by
p2
T =
2m
– Thus, the kinetic energy operator in one-dimension becomes
1 2
T̂x = p̂
2m x 2
1 d
T̂x = i~ (29)
2m dx
2 2
~ d
T̂x = −
2m dx2
In three-dimensions, it becomes
~2
2
∂2 ∂2

∂
T̂ = − + +
2m ∂x2 ∂y 2 ∂z 2
(30)
~2 2
T̂ = − ∇,
2m
where ∇ is called nabla, its a short form of writing the par-
tial first derivative with respect to Cartesian coordinates. To
represent the partial second derivative with respect to the
Cartesian coordinates, square of nabla i.e. ∇2 is used. Thus,
now you know how does kinetic energy operator look like.
• Potential energy operators
– A system acquires potential energy from two sources (1) In-
ternal interaction i.e. interaction between particles within the
system (V̂configuration ) and (2) due to interaction with externally
applied field (V̂interaction ).
– V̂configuration represents the potential energy operator due to
the internal interaction of the particles of the system, which
depends upon the configuration of the system.
– It is a function of Cartesian coordinates of each particle in
the system i.e.
V̂configuration = V ({xi , yi , zi }) (31)
– Since V̂configuration has no real mathematical operator, it is a

multiplicative operator i.e. simple multiplication by a func-
tion of Cartesian coordinates of the particles of the system.
– For example V̂configuration , for a one-dimensional simple har-
monic oscillator, is 21 kx2 , where k is the spring constant (or
force constant) of the spring.
– Now comes V̂interaction . It corresponds to interaction with the
externally applied field. For example, if we apply a field that
oscillates with time then V̂interaction would be say cosωt, where
ω is the frequency of oscillation and t is the time.
• In absence of any external field, the Hamiltonian will simply be
Ĥ = T̂ + V̂ (32)
~2 2
Ĥ = − ∇ + V ({xi , yi , zi }) (33)
2m
20
• If a system consist of particles, which do not interact with each
other – independent particles – then the Hamiltonian will simply
~2
be the kinetic energy operator i.e. Ĥfree = − 2m ∇2 .
1.4.2. Schödinger time-independent equation:
As mentioned earlier, Eq. ?? is a fundamental equation of quan- section
tum mechanics. This is time-dependent Schrödinger equation. It no.
represents the time-evolution of a quantum state of the system.
However, in general, in absence of any external field the state of
the system does not evolve over time and hence for such cases it
is much convenient to use a time-independent version of Eq. ??.
Time-independent Schrödinger equation can easily be obtained from
Eq. ?? using separation of variable technique.1 . Let’s do it. So, we
have
d
ĤΨ(r, t) = i~ Ψ(r, t)
dt
In separation of variable technique, we assume that the function
Ψ(r, t) can be written as a product of two functions each is a function
of one variable only. i.e. Ψ(r, t) = ψ(r)φ(t). Inserting this in time-
dependent Schrödinger’s equation, we can write
d
Ĥψ(r)φ(t) = i~ ψ(r)φ(t)
dt (34)
dφ(t)
Ĥψ(r)φ(t) = i~ψ(r)
dt
Now, since the Hamiltonian Ĥ is time-independent (remember there
is no time-dependent field in Eq. ??), we can write
dφ(t)
φ(t)Ĥψ(r) = i~ψ(r) (35)
dt
Dividing both sides by ψ(r)φ(t), we get
1 1 dφ(t)
Ĥψ(r) = i~ (36)
ψ(r) φ(t) dt
Thus, we have an equation (Eq. ??) whose left hand side is a function
of spatial coordinates (i.e. r) only and right hand side is a function
of time only. Thus, each side should be equal to a constant. Let
this constant be represent by E, which later on can be shown to be
the energy of the state. Thus,
1 dφ(t)
i~ =E
φ(t) dt (37)
φ(t) = e−iEt/~
and
1
Ĥψ(r) = E
ψ(r)
Ĥψ(r) = Eψ(r) (38)

This is time-independent Schrödinger equation.
1.4.3. Nature of Schrödinger’s equation
1
you can know more about separation of variables techniques at (https://tinyurl.com/7c7zkas)
21
• In this section we’ll discuss the nature of the time-independent
Schrödinger’s equation.
Ĥψ(x) = Eψ(x)
~2 2

− ∇ + V (x) ψ(x) = Eψ(x)
2m
~2 d2 ψ(x) (39)
− = (E − V (x)) ψ(x)
2m dx2
d2 ψ(x) 2m
= 2 (V (x) − E) ψ(x)
dx2 ~
• Thus, Schrödinger equation is a second order partial differential
equation.
• Note, in Eq. ?? full derivative is used not partial. This is be-
cause Eq. ?? is written for one-dimensional case. Since in one-
dimensional case there is no other variable a partial derivative
simply becomes full derivate.
• So, what does this second order partial differential equation
says?
• The second derivative of a function is related to the curvature
of the function (https://tinyurl.com/y8l2l573).
• As an approximation, when second derivative of a function is
positive then the graph of the function will be concave up i.e.
^
• similarly, when the second derivative of a function is negative,
the graph of the function will be concave down i.e. _
1.4.4. Conditions imposed on the wavefunctions
We have already discussed this while discussing postulate 1 in sec-
tion 1.4. However, as a revision let’s collect all those conditions
here. So, the conditions imposed on a wavefunction are
• A valid wavefunction should be a single valued, continuous and
quadratically integrable function.
• All the partial first derivatives of a valid wavefunction with re-
spect to the coordinates of each entity in the system should also
be continuous.
• A valid wavefunction should satisfy the boundary conditions for
the system.
• A valid wavefunction should be finite everywhere within the
boundary of the system.
• A valid wavefunction for an electronic system should be anti-
symmetric with respect to the exchange of any two electrons.
1.4.5. Probability interpretation of wave function
• The most fundamental concept in quantum mechanics is wave-
function.
• It contains all the information about the system in a particular
state.
• So, if you have access to the wavefunction of a particular state of
the system that means you can tell everything about the system
in that state.
• This simply means that a wavefunction is loaded with enormous
amount of information.
22
• So, how can you interpret a wavefunction?
• What does a wavefunction really mean?
• Max Born was the first to interpret a wavefunction. His inter-
pretation was a statistical one.
• A wavefunction can be a real, imaginary or a complex function.
But, according to Born’s interpretation, the square modulus of
a wavefunction (Ψ) i.e. |Ψ|2 is always a real number and it
represents the probability density of detecting a particle at a
particular place.
• Thus, |Ψ|2 = Ψ∗ Ψ represents the probability density of detecting
the particle.
• The quantity Ψ∗ Ψdτ then represents the probability of finding
the particle in volume element dτ .
• Ψ is thus a probability distribution function
• Since the particle must be present H ∗somewhere in it’s boundary,
Hthe sum of all probabilities i.e. Ψ Ψdτ should be equal to one.
represents taking integration over the whole boundary of the
system. Z
Ψ∗ Ψdτ = 1 (40)
boundary
Orthogonality and normalization of wavefunctions:

• A wavefunction satisfying Eq. ?? is called a normalized wave-
function.
• A normalized wavefunction simply represents a confirmation
that the particle is somewhere in the limits of integration (i.e.
within the boundary of the system).
• Two wavefunctions ψ and φ are said to be orthogonal when
Z
φ∗ ψdτ = 0 (41)
• As mentioned earlier, orthogonality of wavefunctions represent section

that the two wavefunctions do not share any common space, no.
when plotted on graph.
• Orthogonality also represents a mutual exclusion of the two
states of the system. That means a state does not carry any
information about it’s orthogonal state.
• So, if a system is in one state ψ then you can never measure the
property corresponding to the orthogonal state φ.
• In other words, using the wavefunction ψ one can never calculate
the properties of corresponding to wavefunction φ.
• The quantity Z
φ∗ ψdτ (42)
is called the overlap integral and it represents how much alike

the two states are to each other?
1.5. Particle in a box:
• So far, we have learned the basics of quantum mechanics. Now, it’s
turn to see how can we apply these to some very simple systems.
• These simple systems are ideal systems called model systems.
23
• A model system is designed in such a way that they represent the
most simplified scenario of a real system.
• One of such model systems is particle in a box model.
The following discussion will help us to understand this topic.
What is this particle in a box model?
– Particle in a box is a simple system.
– We consider a one-dimensional region of certain length (say, L)
along x-axis between x = 0 and x = L.
– A constant potential is applied in the region 0 < x < L. For
convenience this constant potential is considered to be 0.
– In regions other than 0 < x < L, infinite potential is applied.
– Finally, we put a quantum mechanical particle of mass m in the
region 0 < x < L.
– Thus, pictorially, particle in a 1D box would look like
Figure 4: Pictorial representation of particle in a 1D box
What real system does a particle in a box model represent?

– Particle in a box actually represents an electron in a linear
molecule.
– Let us suppose a linear conjugated molecule. For example, buta-
1,3-diene (CH2 = CH − CH = CH2 ).
– The particle inside the box in Fig. ?? is actually representative
of the mobile electrons i.e. π-electrons in buta-1,3-diene.
– The length, L of the box in Fig. ?? represents the length of the
molecule i.e. distance between the two end C-atoms.
– The boundary of the box in Fig. ?? represent the two ends of
the molecule.
– This is very obvious that the electrons in a molecule can not
fall out of the molecule when it reaches the end as if some force
forbids the electrons to fall out. This fact is represented by the
infinite potential at the two end of the box in Fig. ??.
– It is also reasonable to consider that the electrons within the
molecule experiences a uniform (a constant) potential. This is
represented by a constant (or for convenience, zero potential)
within the box.
– Thus, you see, particle in a box model can reasonably be used
as a simplified model for a linear molecule with π-electrons i.e.
linear conjugated molecules.
How can we apply quantum mechanical principles to study this
model?
24
– In quantum mechanics, the basic equation is Schrödinger’s equa-
tion.
– At first, we will write down the correct Hamiltonian for the
system that appears in Schrödinger’s equation.
– We will then solve the time-independent Schrödinger equation
for our model.
– Note, we are not interested in time-dependent problem as there
is no time-dependent applied field.
– After solving the time-independent Schrödinger’s equation, we
will get the energy and wavefunction of different states of the
system.
What real properties can we calculate?
– By solving Schrödinger equation, we get the wavefunction and
energy of different states of the system.
– From wavefunctions, we can calculate any observable for our
model system.
– From energies of different states, we can calculate the energy
difference between states, which in basically the excitation en-
ergy.
– From excitation energy, we can calculate the wavelength of light
that can be used for causing a particular transition.
– It is important to keep in mind that particle in a 1D box is a
simplified model and hence we cannot expect it to reproduce
the experimental values of excitation energy or excitation wave-
length or other properties.
– However, it can definitely be used to reproduce the experimen-
tal trend in a property. For example, the variation of excita-
tion wavelength with the increase in length of linear conjugated
molecules.
1.5.1. Setting up of Schrödinger equation for 1D box and solution
Now, you know, what a particle in a 1D box model is and why and
what are we going to do with this model. So, let’s move on
• Hamiltonian for the particle in a 1D box model
According to Eq. ??, the Hamiltonian in one-dimension is given
by
~2 d2
Ĥ = − + V (x)
2m dx2
Since potential for a particle in a 1D box is infinite everywhere
except in the region 0 < x < L, the particle cannot exist outside
this region. Therefore, we should only consider the Hamiltonian
in this region (0 < x < L), which would be
~2 d2
Ĥ = − (43)
2m dx2
• Solving Schrödinger’s equation for particle in a 1D box:
– As mentioned earlier, the particle does not exist outside the section
region 0 < x < L. Therefore, there is no meaning of wave- no.
function outside this region.
– If Ψ(x) and E be the wavefunction and energy of the parti-
cle inside the box, the Schrödinger’s equation inside the box
25
would simply be
~2 d2
− Ψ(x) = EΨ(x), 0 < x < L
2m dx2
d2 2mE
Ψ(x) + Ψ(x) = 0, 0 < x < L (44)
dx2 ~2 √
d2 2 2mE
Ψ(x) + k Ψ(x) = 0, k = , 0<x<L
dx2 ~
– This is a standard second order homogeneous differential equa-
tion.
– Such equations have a general solution of the form Ψ(x) =
C1 eikx + C2 e−ikx , which is equivalent to Ψ(x) = Acos(kx) +
Bsin(kx), where C1 , C2 , A and B are constants.
– We can proceed with any of the two forms. Here, we will deal
with the later form.
– The constants A and B can be determined by applying the
boundary conditions and then by normalizing the wavefunc-
tion.
– Applying boundary conditions:
Boundary condition 1: At x = 0, Ψ(x) = Ψ(0) = 0. Putting
this in Eq. ??.
A=0 (45)
With this, the wavefunction becomes
Ψ(x) = Bsin(kx) (46)
The constant can be obtained by normalizing the wavefunc-
tion. But, this we’ll do a bit later. Let us first apply the
second boundary condition.
Boundary condition 2: At x = L, Ψ(x) = Ψ(x = L) = 0.
Putting this condition in Eq. ??.
Bsin(kL) = 0 (47)
Since, B 6= 0 (otherwise the wavefunction Eq. ??, will become
zero inside the box). Thus, Eq. ?? gives
sin(kL) = 0
(48)
=⇒ kL = nπ,
where n = 0, 1, 2, 3, . . . . It is important to note that n = 0 is
also not allowed, because it will also make the wavefunction
zero inside the box. This suggests that the states of a particle
in a 1D box are quantized. n = 1 corresponds to ground
state, n = 2 is the first excited state and so on. Putting the
expression for k in Eq. ?? gives
√
2mE
L = nπ, n = 1, 2, 3, . . .
~ (49)
n2 ~2 π 2
E=
2mL2
Thus, the expression for the energy of a particle in a 1D box
is
n2 h2
E= (50)
8mL2
26
– Now, let’s find out the constant B in Eq. ??. The condition
for normalization of wavefunction for particle in a 1D box is
ZL
Ψ(x)2 dx = 1
0
ZL
nπx
B 2 sin2 dx = 1
L
0
ZL
B2

2nπx
1 − cos dx = 1
2 L
0
Since, n is an integer, the result of integration of cos 2nπx

L will
always be zero. So
B 2L
=1
2 r
2
B=
L
This makes the wavefunction (Eq. ??), for a particle in a 1D
box as
r
2 nπx
Ψ(x) = sin (51)
L L
– The wavefunction and energy for the ground state i.e. the
state corresponding to n = 1 are
r
2 πx
Ψgs (x) = sin
L L
(52)
h2
Egs =
8mL2
• More fun with particle in a box model

So, now, we know both the wavefunction and energy of different
states of a particle in a 1D box. Now, based on our previous
learnings, let us do some more fun with these wavefunction and
energies.
– The first thing we can do is to see how the wavefunction varies
along x-axis. We can also check the variation of probability
density. For this, we can directly plot Ψ(x) and |Ψ(x)|2 . The
plots are shown in Fig. ??. For this figure, we have considered
a box of length 2Å. There are few interesting things to note
in Fig. ??.
i. Both the wavefunction and probability density are always
zero at the two ends of the box i.e. at x = 0 and x = L.
ii. Nodes are the points where both the wavefunction and the
probability density have zero value. That means the parti-
cle never occupy these points.
27
Variation of PIB 1D n = 1 wavefunctions with x Probability density n = 1
1 1
n=1 n=1
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
2
1 (x)|
1 (x)
0.5 0.5
0.4 0.4
|
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Variation of PIB 1D n
x(=
Å)2 wavefunctions with x x(density
Probability Å) n=2
1 1
0.8 0.9
0.6 0.8
0.4 0.7
0.2 0.6
2
2 (x)|
2 (x)
0 0.5
0.2 0.4
|
0.4 0.3
0.6 0.2
n=2
0.8 0.1
n=2
1 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Variation of PIB 1D nx(=Å)
3 wavefunctions with x Probabilityx(density
Å) n=3
1 1
0.8 0.9
0.6 0.8
0.4 0.7
0.2 0.6
2
3 (x)|
3 (x)
1 4
0 0.5
0.2 0.4
|
0.4 0.3
0.6 0.2
n=3
0.8 0.1
n=3
1 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
x(Å) x(Å)
Figure 5: wavefunctions and probability density for particle in a 1D box

2 5
iii. Within the box, there is no node for ground state wave-
function.
iv. For the first exited state i.e. n = 2, there is one node within
the box and for the second excited state i.e. n = 3, there
are two nodes within the box.
v. In general, for the mth excited state, there exist m nodes
3 6
within the box. Note, for mth excited state, n = m + 1.

Weird quantum world
Did you notice something weird? No! Lets read points
ii and iv again. If the particle never exists at the nodes
and there exist nodes within the box then how the par-
ticle moves from one side to the other side of the box?
Can you explain this? It’s really very hard to realize
it. We can simply say that this is the nature of a quan-
tum particle. Since the energy and other properties of
a quantum particle is not continuous (that means these
are quantized), the movement of such particles and hence
their spatial existence are also not continuous but dis-
crete. The nodes can be considered as the forbidden
regions for the particle. When we quantize the energy of
a particle, we do so with it’s existence too.
Numerical illustration of quantum weirdness:

∗ To have more feelings about quantum weirdness, let us
do some calculations. Fig. ?? shows that there is a node
at x = 1 for first excited state of a particle in a 1D box.
∗ So, to detect that the particle goes from left side of the
28
node to the right side without passing through the node,
let us find out the probability of finding the particle in a
small volume element slightly left to the node (between
x = 0.9Å and x = 0.99Å) and a small volume element
slightly right to the node (between x = 1.01Å and x =
1.1Å).
∗ In section 1.4.5, we have seen that the probability of find-
ing a particle between two points x = x1 and x = x2 is
given by
x=x
Z 2
Ψ∗ (x)Ψ(x)dx
x=x1
∗ The wavefunction of the particle in first excited state is

Ψn=2 (x) = sin(πx). [Note, length of the box is L = 2Å
and for first excited state n = 2.]
∗ Thus, the probability of finding the particle slightly to
the left of the node i.e. between x = 0.9Å and x = 0.99Å
is
x=x
Z 2 Z0.99
Ψ∗ (x)Ψ(x)dx = sin2 (πx)dx = 0.00322
x=x1 0.9
Similarly, the probability of finding the particle slightly

to the right of the node i.e. between x = 1.01Å and
x = 1.1Å is
x=x
Z 2 Z1.1
Ψ∗ (x)Ψ(x)dx = sin2 (πx)dx = 0.00322
x=x1 1.01
∗ Thus, we see that there is a finite probability of finding

the particle immediately to the left or to the right of the
node. But is zero at the node. This confirms that the
particle moves from one side to the other side of node
without ever existing at the node.
29
Another quantum weirdness
There is another weird thing in Fig. ??.
∗ Let us have a look at the probability density plot

for ground state.
∗ This plot tells us, how probable is it to find the

particle at a particular point in the box.
∗ As the figure suggests, the probability of finding

the particle is maximum at the center of the box.
∗ It seems that the particle is trying to avoid the

boundary (as if they fear of something at the
boundary). As we move towards the boundary,
the probability decreases.
∗ This is weird. Classically, the probability of finding

the particle should be equal at any point in the box.
∗ This is another weird nature of quantum particles

and is completely because of their quantum me-
chanical nature.
OK, we have talked enough about weirdness of a particle in a

1D box. Let us now discuss some other interesting features.
– Orthogonality of two states:
∗ We know from previous sections that two orthogonal states
do not share any common information.
∗ So, it will be fun to know, which two states of particle in a
1D box are orthogonal to each other?
∗ For this purpose let us two consider two different states of
the system, say Ψm (x) and Ψn (x) states and evaluate the
overlap integral between the two.
∗ The overlap integral between the two states is given by
(From Eq. ??)
x=L
Z x=L
Z
mπx nπx
Ψm (x)Ψn (x)dx = sin sin x
L L
x=0 x=0
x=L x=L
(m − n)πx
Z Z
1 1 (m + n)πx
= cos dx − cos dx
2 L 2 L
x=0 x=0
L
(m − n)πx

L L (m + n)πx
= sin − sin
2(m − n)π L 2(m + n)π L 0
L L
= sin((m − n)π) − sin((m + n)π)
2(m − n)π 2(m + n)π
Since both m and n are integers, each term on right hand
side will be zero. Therefore, for any two different states of
30
a particle in 1D box,
x=L
Z
Ψm (x)Ψn (x)dx = 0
x=0
Thus, the states of a particle in a 1D box are orthogonal

to each other.
– Studying physically observable quantity of real systems

∗ As mentioned before, particle in a 1D box is a simplified
model and hence as such it cannot reproduce an experimen-
tal result. However, it can be used to study an experimental
trend.
∗ In this section, we will see whether or not our particle
in a 1D box model can reproduce the experimental trend
of variation of excitation wavelength in linear conjugated
molecules.
∗ For particle in a 1D box, the excitation energy for a tran-
sition from mth state to nth state is given by,
n2 h2 m2 h2 2 2 h2
∆Emn = En −Em = − = (n −m ) (53)
8mL2 8mL2 8mL2
The wavelength (λmn ) corresponding to excitation energy
∆Emn is given by
hc
∆Emn = , (54)
λmn
where c is the speed of light in vacuum. Combining Eqs. ??
and ??, we get
8mcL2
λmn = 2 (55)
(n − m2 )h
Thus, for a transition from ground state (m = 1) to the
first excited state (n = 2), we can write
8mcL2
λ12 = (56)
3h
Since, m, c and h are fundamental constants, Eq. ?? reflects
that the excitation wavelength should increase with the in-
crease in length of the box (or length of linear conjugated
alkenes)
∗ An experimental study of UV-Visible spectra of several lin-
ear conjugated alkenes shows the following results
Molecule Wavelength
Ethylene 163
Butadiene 217
Hexatriene 268
Octatetraene 304
Decapentaene 328
31
∗ It is clear that experimentally the excitation wavelength
of linear conjugated alkenes gradually increases with the
increase in chain-length, which is also predicted by particle
in a 1D box model.
∗ Thus, we see that particle in a 1D box model can be used
to predict an experimental trend in excitation wavelength
in linear conjugated alkenes.
Actual comparison
Problem: Buta-1,3-diene is a conjugated molecule. It has
a structure CH2 = CH − CH = CH2 . If effective length
of the molecule be 4Å then by using particle in a 1D box
model, calculate the excitation energy for transition from
ground state to the first excited state in buta-1,3-diene.
Compare your result with the experimental value of 217nm.
Solution:
Putting the values of m = 9.1 × 10−31 kg, h = 6.626 ×
10−34 J.Sec, c = 3.0 × 108 m and L = 4 × 10−10 m in Eq. ??,
we get
8 × 9.1 × 10−31 kg × 3.0 × 108 m.sec−1 2

λ12 = L
6.626 × 10−34 J.Sec
λ12 = 32.961 × 1011 (4 × 10−10 )2 m, (L is in m.)
λ12 = 527.4 × 10−9 m = 527.4nm
This wavelength is much larger than the experimental

value. Thus, because of very simple nature, particle in
a 1D box cannot really reproduce the experimental value.
But as shown in previous section, it can be used to predict
the experimental trend.
1.5.2. Free particle

A concept closely related to our particle in a 1D box is free particle.
As the name suggest, a free particle is on which is not acted upon
by a field. Thus, if you remove the two infinite potentials at the two
points (i.e. at x = 0 and x = L) in a particle in a 1D box then it
turns to be a free particle.
• Schrødinger equation, wavefunction and energy of a free particle
– A free particle has the same Schrødinger equation as particle
in 1D box i.e. Eq ?? except that there is no limit on x.
– Thus, for a free particle,
p
2 2mEfp
d 2
Ψ fp (x) + k Ψ
fp fp (x) = 0, k fp = (57)
dx2 ~
The subscript “fp” is used to represent that the wavefunction
and the energy are for a free particle.
– Eq. ?? has the same solution, as the particle in a 1D box i.e.
Ψfp (x) = C1 eikfp x + C2 e−ikfp x .
– Note, there is no limit on x that means there is no boundary
32
condition. The quantity
Z+∞
Ψ∗fp (x)Ψfp (x)dx (58)
−∞
is infinite and hence the free particle wavefunctions are not

normalizable.
– If you remember, we get the energy expression for particle in a
1D box by normalizing the corresponding wavefunction. Since
for a free particle, we cannot normalize the wavefunction, an
explicit energy expression cannot be obtained.
– However, we can have some idea about the energy if We can
put one obvious condition on Ψfp (x). The obvious condition is
that Ψfp (x) should be finite everywhere, even when x → ±∞.
– Now, if that is the case then Efp cannot be negative. Because,
Efp < 0 =⇒ kfp = imaginary =⇒ Ψfp (x) becomes infinity
as x → +∞.
– Thus, energy of a free particle should always be positive.
• Comparison of eigenfunctions and eigenvalues of particle in a
1D box and a free particle
– The eigenfunctions for particle in a 1D box is a sine function
but that of a free particle is a linear combination of sine and
cosine functions.
– The eigenfunctions of particle in a 1D box is normalizable but
that of a free particle is not.
– The eigenvalues i.e energy for a particle in a 1D box varies
inversely with the square of length of the box but no such
condition can be derived for a free particle, because there is
no boundary.
– The energy of particle in a 1D box is quantized (depends on
the quantum number n) but that of a free particle is not, in
fact there is no energy expression for a free particle.
1.5.3. Properties of PIB wavefunctions (normalization, orthogonality, prob-
ability distribution)
These topics have already been discussed previously.
1.5.4. Expectation values of x, x2 , px , and p2x for a particle in a 1D box and
their significance in relation to the uncertainty principle
• As mentioned in postulate 5 of quantum mechanics, the average
value (also called expectation value) of a quantity A correspond-
ing to the operator Â in a normalized state Ψ is given by
Z
hAi = Ψ∗ ÂΨdτ, (59)
all space
“all space” represents the boundary condition for the system.

• Using Eq. ??, let us find out the expectation values of some
important quantities like x, x2 , px and p2x .
• But before doing this you must know what these quantities are
and why should you do this?
33
• hxi and hpx i are the expectation values of the position and linear
momentum of the particle. In simple words, they represent the
average position and average linear momentum of the particle.
• Similarly, hx2 i and hp2x i are the average of the square of the
position and momentum of the particle.
• These quantities are basically related to the standard deviation
of position and linear momentum i.e. ∆x and ∆px terms ap-
peared in the expression for Heisenberg Uncertainty principle.
• The said relationship is given by
p
∆A = hA2 i − hAi2 (60)
• So, if we know these four expectation value, we can check if

Uncertainty principle is valid for the particle or not.
Now you know what these four expectation values are and why we
want to calculate these values for particle in a 1D box. So, let’s do
it.
• Calculating hxi for particle in a 1D box:
ZL
hxi = Ψ∗n (x)x̂Ψn (x)dx
0
ZL r r
2 nπx 2 nπx
= sin x sin dx
L L L L
0
ZL
1 2nπx
= 1 − cos xdx
L L
0
ZL
1 2nπx
= x − xcos dx
L L
0
2 L
L2

1 x L 2nπx 2nπx
= − xsin − 2 2 cos
L 2 2nπ L 4n π L 0
L
hxi =
2
(61)
Thus, the average position of the particle is at the middle of the

box. This can also be predicted from the ground state proba-
bility density plot in Fig. ??.
34
• Calculating hx2 i for particle in a 1D box:
ZL
hx2 i = Ψ∗n (x)x̂2 Ψn (x)dx
0
ZL r r
2 nπx
2 2 nπx
= sin x sin dx
L L L L
0
ZL ZL
1 2nπx 1 2nπx
= 1 − cos x2 dx = x2 − x2 cos dx
L L L L
0 0
3
2xL2 2L3

1 x L 2 2nπx nπx 2nπ
= + x sin + 2 2 cos − 3 3 sin
L 3 2nπ L 4n π L 8n π L
2 2
L L
hx2 i = + 2 2
3 2n π
(62)
• Calculating hpx i for particle in a 1D box:
ZL
hpx i = Ψ∗n (x)p̂x Ψn (x)dx
0
ZL r nπx r
2 d 2 nπx
= sin −i~ sin dx
L L dx L L
0
ZL
2inπ~ nπx nπx
=− 2 sin cos dx (63)
L L L
0
ZL
inπ~ 2nπx
=− 2 sin dx
L L
0
L
inπ~ L 2nπx
=− 2 × cos
L 2nπ L 0
hpx i = 0
We see that the expectation value of linear momentum for a

particle in a 1D box is zero. This is obvious, because since
we did not put any restriction on the direction of movement of
the particle, it can move both in positive (towards x = L) or
in negative direction (toward x = 0). On average, these two
opposite linear momenta cancel out each other.
35
• Calculating hp2x i for particle in a 1D box:
ZL
hp2x i = Ψ∗n (x)p̂2x Ψn (x)dx
0
ZL r nπx 2
r
2 2 d 2 nπx
= sin −~ sin dx
L L dx2 L L
0
2 2 2 ZL
2~ n π 2
nπx
= sin dx
L3 L (64)
0
ZL
~2 n2 π 2

2nπx
= 1 − cos dx
L3 L
0
2 2 2
L
~nπ L 2nπx
= x− sin
L3 2nπ L 0
2
nπ~
=
L
• Since, we now have all the four expectation values hxi, hx2 i, hpx i
and hp2x i, let’s calculate the uncertainty in position and momen-
tum of the particle in a 1D box.
• Calculating ∆x
p
∆x = hx2 i − hxi2
r
L2 L2 L2
= + 2 2−
r3 2n π 4
1 1
=L + 2 2
12 2n π
• Calculating ∆px
p
∆px = hp2x i − hpx i2
s 2
nπ~
= −0
L
nπ~
=
L
• Calculating ∆x∆px
r
1 1 nπ~
∆x∆px = L + 2 2×
r12 2n π L
1 1
= nπ~ + 2 2
12 2n π
Even for minimum value of n i.e. n = 1
r
1 1 ~
∆x∆px = π~ + 2 = 1.14~ >
12 2π 2
~
Thus, for any state of a particle in a 1D box, ∆x∆px > 2 i.e.
Heisenberg uncertainty principle is valid.
36
1.5.5. Extension of PIB to 2D and 3D
• Particle in a 1D box is a simplified model for linear conjugated
molecule.
• However, a molecule is not one dimensional.
• So, a better model would be a particle in a 2D or 3D box.
• That’s why, we need an extension of our model to 2D and 3D.
• This is very simple. We don’t even need to solve the Schrødinger’s
equation in 2D or 3D.
• Why? The reason is explained in the following.
Wavefunction of particle in a 2D and 3D box
• We have seen that the eigenfunction of T̂x operator (which

is basically the hamiltonian for particle q
in a 1D box along
x-axis) is a function of x variable only ( L2 sin nπx
L ).
• In stead of considering the box along x-axis, if we consider
it along y-axis then the hamiltonian will be T̂y and the
eigenfunction will be a function of y variable only.
• Thus, the eigenfunction of T̂x behaves as a constant, when
it is acted upon by T̂y and that of T̂y behave as a constant
for T̂x operator.
• Hence, a product of eigenfunctions of the two operators
will serve as an eigenfunction for both the operators.
• So, the solution for particle
q in a 2D box q (along x and y
2 nx πx 2 ny πy
axes) can be written as Lx sin Lx × Ly sin Ly
• Similarly,
q for 3D
q box, the solution
q will be
2 nx πx 2 ny πy 2 nz πz
Lx sin Lx × Ly sin Ly × Lz sin Lz
• Lx , Ly , and Lz are the length of the box along the three
Cartesian axes and nx , ny , and nz are the respective quan-
tum numbers.
• OK, we have got the wavefunction for particle in a 2D and 3D

boxes very easily. What will be the eigenvalues then?
Engery of particle in a 2D or 3D box
• This is also very simple. The eigenvalue will simply be the
sum of the eigenvalues of the T̂i (i ≡ x, y, z) operators.
• Let us verify it.
• Let Ψx , Ψy , and Ψz be the eigenfunctions of the operators
T̂x , T̂y , and T̂z with eigenvalues Ex , Ey , and Ez respectively.
Thus

T̂x + T̂y + T̂z Ψx Ψy Ψz = T̂x Ψx Ψy Ψz + T̂y Ψx Ψy Ψz + T̂z Ψx Ψy Ψz
= Ψy Ψz T̂x Ψx + Ψx Ψz T̂y Ψy + Ψx Ψy T̂z Ψz
= Ex Ψy Ψz Ψx + Ey Ψx Ψz Ψy + Ez Ψx Ψy Ψz
= (Ex + Ey + Ez ) Ψx Ψy Ψz
• Thus, we see, (1) the wavefunction for a particle in a 2D or

3D box will simply be a product of the wavefunctions for particle
in a 1D box in different directions and (2) the corresponding
37
eigenvalue will be the sum of the eigenvalues for the particle in
a 1D box in different directions.
Wavefunction and energy – particle in a 2D and 3D
box
In 2D box
For rectangular box (Lx =6 Ly )

s
22 nx πx ny πy
Ψnx ,ny = sin sin
Lx Ly Lx Ly
! (65)
n2x n2y h2
Enx ,ny = +
L2x L2y 8m
For square box (Lx = Ly = L)

r
22 nx πx ny πy
Ψnx ,ny = sin sin
L2 L L (66)
h2
Enx ,ny = n2x + n2y
8mL2
In 3D box
For cuboid box (Lx = 6 Ly 6= Lz )

s
23 nx πx ny πy nz πz
Ψnx ,ny ,nz = sin sin sin
Lx Ly Lz Lx Ly Lz
! (67)
n2x n2y n2z h2
Enx ,ny ,nz = + +
L2x L2y L2z 8m
For cubic box (Lx = Ly = Lz = L)

r
Ψnx ,ny ,nz = sin sin sin
L3 L L L (68)
h2
Enx ,ny ,nz = n2x + n2y + n2z
8mL2
1.5.6. Concept of degeneracy

• Two different states having same energy are called degenerate
states.
• In particle in a 1D box, it is obvious from Eq. ?? that no two
states can have the same energy – because no two states can
have same value for the quantum number n.
• However, from Eqs. ??, ??, ?? and ?? one can easily see that
particle in a 2D or in a 3D box can have same energies in two
different states – because all the three quantum numbers nx , ny ,
and nz can have an integer value (1, 2, 3, . . . )
• As an example, Let us consider the energies of nx = 1, ny = 2
(in short (1, 2)) and nx = 2, ny = 1 (in short (2, 1)) states of a
particle in a square box (Eq. ??). Both of these states have an
38
2
5h
energy of 8mL 2 and hence are degenerate.
• Similarly, in a cubic 3D box, the states, for example (1, 1, 2), (1, 2, 1), (2, 1,
are also degenerate.
• These degeneracies arise merely because of permutations in val-
ues of the quantum numbers.
• However, Eqs. ?? and ?? indicate that additional degeneracies
are also possible due to ratio of the quantum number to the
length of the sides of the box in different directions.
• For example, for a rectangular box with Lx : Ly = 2 : 1, the
states (2, 5) and (10, 1) are degenerate. Check if, for this box,
the pair of states (1, 4), (7, 2) and (1, 6), (9, 4) are degenerate or
not?
• Similar, if the box is such that Lx : Ly = 1 : 2 then the states
(2, 2) and (1, 4) will be degenerate. Check if, for this box, the
pair of states (1, 6), (3, 2) and (1, 8), (4, 2) are degenerate or not?
• Degeneracy basically reflects the symmetry in a system. The
more symmetrical a system is the more is the number of degen-
erate levels it can have.
Not in syllabus: Particle in a 1D box with a non-uniform po-

tential
• So far, we have considered a uniform potential within the box (for
our convenience, we have considered it to be zero, V = 0).
• What will happen if the particle is subjected to a non-uniform

potential inside the box? In this section, we will address this
question.
• In simple words, applying a potential inside the box simply means

applying a field.
• For example, suppose you are riding your bicycle on a flat smooth
road without any pit or speed-breaker or a turn or traffic. This
means you are in a uniform potential (no disturbance).
• Now suppose, there are speed-breakers at different places on the

road or there is traffic on the road.
• The speed-breakers or the traffic puts extra conditions on your

cycling. You become more cautious during cycling. This reflects
that you are cycling in a non-uniform condition ≡ non-uniform
potential.
• So, applying a non-uniform potential simply means creating trou-

ble for the movement of the particle.
• This means, in a non-uniform potential there will be extra restric-

tion(s) on the particle.
• Let us start with a very simple potential – a sinusoidal potential

sinx, between 0 < x < L. For simplicity, we consider L = π
2. Quantum Chemistry II
39
2.1. Simple Harmonic Oscillator
2.1.1. What is an oscillator, a harmonic oscillator and a simple harmonic

oscillator?
We can start our discussion with the word ‘Oscillator’. An oscillator
is simply anything that undergoes a periodic motion that means it
goes forth and back about a fixed position. The fixed position is
also called the equilibrium position and is nothing but the position
of the system when it is not acted upon by any external force. For
example, if you hit a hanging fruit softly (so, that it does not fall
from the branch) then it starts oscillating.
A harmonic oscillator is any system which when displaced from its
equilibrium position experiences a restoring force that is directly
proportional to the displacement. For example, let us consider a
spring. If you press a spring a tension is generated in it and when
you release the pressure the spring immediately relaxes and jumps in
a direction opposite to the direction of application of force. Another
Spring at
equilibrium
Displacement
𝒙
Stretched Applied force

spring
Restoring
force (𝑭)
example of a harmonic oscillator is a pendulum. If you drag the bob

of a pendulum from its equilibrium position and release it then the
bob will move towards its equilibrium position.
Displacement in
this direction
𝑥
in
F)
r c e(
o
Bob
i ng F ction
Equilibrium r e
sto dir
position Re this
A simple harmonic oscillator is a harmonic oscillator that is not

acted upon by an external force. That means, you displace the
harmonic oscillator from its equilibrium position and release it freely
without applying any extra force.
2.1.2. Why do we study simple harmonic oscillator in quantum mechanics?
What real system does it represent?
We know that in a molecule, the atoms are bonded with each other.
40
These bonds do not remain static. They always oscillates. The
nature of these oscillations can be very simple (as in the case of
di-atomic molecules) or very complex (as in case of molecules with
large number of atoms). In order to study these oscillations (also
called bond vibration) the problem of simple harmonic oscillator
serves as the simplest model.
Compressed
Equilibrium position
Stretched
2.1.3. What problem are we going to solve?

Let us first define our system. Let our system consists of a mass m
attached to a wall with a weightless spring of equilibrium length l
along x−axis, as shown in figure ??. Now, if the spring is stretched
𝒙=𝟎 𝒙=𝒙
Spring at m1
equilibrium
Displacement
𝒙
Stretched m1
spring
Restoring
force (𝑭)
Figure 6: Our one-dimensional simple harmonic oscillator.
by moving the mass by a distance x and then released freely, the

system will start exhibiting simple harmonic oscillations about x =
0. Let the frequency of oscillation be ν.2 Our target is to study the
system, for which, we will (i) write down the Hamiltonian for the
system and
(ii) setup the Schrödinger equation for it.
(iii) we are not going to solve it3 but we will directly study the
characteristic features of the energies and wavefunctions of different
states of our simple harmonic oscillator.
2.1.4. Hamiltonian for a simple harmonic oscillator in one dimension
In a simple harmonic oscillator, the restoring force is directly pro-
portional to the displacement from equilibrium position. If F be the
restoring force and x be the displacement from equilibrium position,
2
As mentioned above, simple harmonic oscillation/motion is a periodic motion that means the system moves from
one side of equilibrium position to the other side. When the system starts from one side (say, right side of x = 0)
it crosses the equilibrium position and goes to the other side (left side of x = 0), then again when it returns back
to its previous side (left side of x = 0) then it is said that one oscillation is completed. The number of oscillations
completed by the system in one second is called frequency of oscillation. It has a unit of sec−1 or Hertz (Hz).
3
This is a little bit complicated problem. That’s why we’ll not solve the Schrödinger equation for simple harmonic
oscillator.
41
then
F ∝x
(69)
F = −kx,
where k is the proportionality constant and is also called force con-

stant. This force constant is related to the mass of the system and
frequency of oscillation.
The relation between force constant (k), linear frequency of oscilla-
tion (ν) and mass (m) of the system is given by
r
1 k
ν=
2π m
r (70)
k
ω= , ω = 2πν = Angular frequency of oscillation.
m
We know that the Hamiltonian is given as
Ĥ = T̂ + V̂ , (71)
where T̂ and V̂ are the kinetic and potential energy operators re-
spectively. The kinetic energy operator has a universal expression
~2 d2
T̂ = −
2m dx2
But the potential energy operator depends on the system under
study. For simple harmonic oscillator, the potential energy operator
has to be obtained from the restoring force (the only expression we
know so far).
We know, for a conservative force i.e. a force which depends only
upon the position coordinates, potential energy is given by
dV
F =−
dx
Z
V =− F dx
Since, the restoring force in a simple harmonic oscillator is also

conservative in nature, the potential energy operator can be written
as
Zx
1
V̂ = − (−kx)dx = kx2 (72)
2
0
Thus, the Hamiltonian for a simple harmonic oscillator is
~2 d2 1 2
Ĥ = − + kx
2m dx2 2 (73)
~2 d2 1
Ĥ = − 2
+ mω 2 x2
2m dx 2
42
mass m replaced by reduced mass µ
Note that, if the system consists of more than one particle then
the mass (m) should be replaced by the reduced mass (µ) of
the system. For example, if our system consists of two masses
m1 and m2 attached with each other by the spring then the
reduced mass (µ) of the system will be
1 1 1
= +
µ m1 m2
m1 m2
µ=
m1 + m2
The concept of reduced mass is used to reduce a many-body
problem to a single body problem.
2.1.5. Setting up of the time-independent Schrödinger equation

The general time-independent Schrödinger equation in one-dimension
is given by
Ĥψv (x) = Ev ψ(x), (74)
where Ĥ is the Hamiltonian of the system and ψv (x) and Ev are the
wavefunction and energy of v th state of the system. As this model
system is used to study vibrations in molecules, here the quantum
number is represented by v.
Thus, for a 1D simple harmonic oscillator, we can write
~2 d2

1
− + mω 2 x2 ψv (x) = Ev ψ(x) (75)
2m dx2 2
2.1.6. Solution of the time-independent Schrödinger equation for one-dimensional
simple harmonic oscillator.
Wavefunctions of simple harmonic oscillator:
The general solution of Eq. ?? is given by
1 2 2
ψn (x) = Nv · Hv (αx) · e− 2 α x
, v = 0, 1, 2, . . . (76)
where r
α
Nv = (77)
2n n!π 1/2
is the normalization constant,
r
mω
α=
~
and Hv (αx) is a polynomial expression called Hermite polynomial.4
Note that the vibrational quantum number v can have any positive
integer values including 0. The state with v = 0 is called the ground
state, v = 1 is the first excited state and so on.
The value of Hermite polynomial for v = 0 and v = 1 states are
H0 (αx) = 1; H1 (αx) = 2αx (78)

4
The general expression for Hermite polynomial is given by
v 2 dn −y2
Hv (y) = (−1) · ey · e
dy n
43
Hermite polynomials in Eq. ??
Problem: From the general expression of Hermite polynomial,
2 dn −y2
Hv (y) = (−1)v · ey · e (79)
dy n
prove that Eq. ?? is true.
Solution: For v = 0, Eq. ?? becomes
d0 −y2
0 y2
H0 (y) = (−1) · e · 0 e
dy
d0
dy 0 simplyrepresents no-derivative. That means the function
−y 2
e remains intact. Thus,
2 2
H0 (y) = ey · e−y = 1
or, H0 (αx) = 1.
Now, for v = 2, Eq. ?? becomes
2 d 2
H1 (y) = (−1)1 · ey · e−y
dy
2

y y2
= −e × −2ye
= 2y
As y = αx, H1 (αx) = 2αx
Wavefunctions for ground and first excited states.

Using the above informations about the normalization con-
stants (Eq. ??) and Hermite polynomials (Eq. ??), fill the miss-
ing parts in the following to derive the ground state (v = 0)
and first excited state (v = 1) wavefunctions for simple har-
monic oscillator.
Wavefunction for ground state (v = 0):
1 2 2
ψ0 (x) = · · e− 2 α x
r (80)
α − 12 α2 x2
ψ0 (x) = · e
π 1/2
Wavefunction for first excited state (v = 1):
1 2 2
ψ1 (x) = · · e− 2 α x
r (81)
2α3 − 12 α2 x2
ψ1 (x) = · x · e
π 1/2
Variation of ψ0 (x) and ψ1 (x) with x.

We know from the previous discussions that the wavefunction rep-
resents the probability amplitude and square of the wavefunction
represents the probability density. Let us see how does these two
quantities for ground and first excited states of simple harmonic
44
oscillator vary with the displacement x.
��
��
��
��
��
��
��
��
��
��
��
��
� �
Figure 7: Variation of ψ0 (x), ψ1 (x), ψ02 (x) and ψ12 (x).
Characteristics of the plots

• Number of nodes in ψ0 (x) and ψ1 (x)
There is no node in the ground state but there is one in the
first excited state. This can easily be predicted also from the
expressions of the wavefunctions (Eqs ??, ??). The node in first
excited state occurs at x = 0 i.e. at equilibrium position of the
particle.
• Most probable position of the particle in ground state

The most probable position of finding the particle in ground
state is at x = 0 i.e. at the equilibrium position of the particle.
This is counter-intuitive. Since the particle is exhibiting simple
harmonic motion, classically, the kinetic energy of the particle is
maximum at x = 0 and hence the particle spends least time at
the equilibrium. Similarly, since the kinetic energy of particle is
minimum at the two extreme points, the particle is supposed to
spend maximum time at the two extreme points. However, this
is true only for classical case. In quantum mechanics, things are
different and the most probable position of finding the particle
at the equilibrium is a quantum mechanical characteristic of the
system.
Show mathematically that the most probable position of find-

ing the particle exhibiting simple harmonic motion in ground
state is x = 0.
The most probable position of finding the particle exhibiting

simple harmonic motion in ground state is obtained in two
steps – (A) by taking derivative of ψ02 (x) with respect to x
and setting the same to zero and then (B) finding the value of
x obtained in step A for which the second derivative of ψ02 (x)
with respect to x is negative.
45
Step A:
d 2
ψ (x) = 0
dx 0
r 2
d α − 1 α 2 x2
e 2 =0
dx π 1/2
α d −α2 x2
e =0
π 1/2 dx
α 2
−α2 x2
× −2α x × e =0
π 1/2
−α2 x2 2α3
−xe = 0, as, 1/2 6= 0
π
This equation has three roots – (i) x = 0 and (ii & iii) x =
±∞.
Step B:
d2 2 2α3 n −α2 x2
2 −α2 x2
o
ψ (x) = − 1/2 e + x −2α xe
dx2 0 π
2α3 2 2
= − 1/2 1 − 2α2 x2 e−α x

π
Now,
d2 2 2α3
At x = 0, 2 ψ0 (x) = − 1/2 < 0
dx π
2
d
At x = ±∞, 2 ψ02 (x) = 0
dx
Thus, the probability of finding the particle will be maximum
at x = 0.
• Most probable position of the particle in first excited state
Figure ?? clearly shows that the probability of finding the parti-
cle in its first excited state is maximum at two equidistant points
on the two sides of the equilibrium position.
Show mathematically that there are two most probable posi-

tions of finding the particle exhibiting simple harmonic motion
in its first excited state.
We’ll follow the same steps as we did for ground state.

Step A:
d 2
ψ (x) = 0
dx 1 !
r 2
d 2α3 − 1 α2 x2
xe 2 =0
dx π 1/2
2α3 d 2 −α2 x2
xe =0
π 1/2 dx
2α3 n −α2 x2 2

2 −α2 x2
o
× e × (2x) + x × −2α xe =0
π 1/2
2 2 4α3
x 1 − α2 x2 e−α x = 0,

as, 1/2 6= 0
π
46
This equation has five roots – (i) x = 0, (ii & iii) x = ± α1 and
(iv & v) x = ±∞.
Step B:
d2 2 4α3 h 2 2
−α2 x2 n 2 2
−α x 2

ψ (x) = 1 − α x e + x e 0 − 2α x
dx2 1 π 1/2
2 2
2 −α2 x2
oi
+ 1−α x −2α xe
4α3 2 2
= 1/2 1 − 5α2 x2 + 2α4 x4 e−α x

π
Now,
d2 2 4α3
At x = 0, ψ (x) = 1/2 > 0 Minima
dx2 1 π
d2 2
At x = ±∞, ψ (x) = 0 Inflection point
dx2 1
1 d2 2 8α3
and at x = ± , ψ (x) = − 1/2 < 0 Maxima
α dx2 1 π e
Thus, the particle in first excited state has two most probable
positions equidistant from the equilibrium position.
Energies of different states of simple harmonic oscillator:

The energy of the v th state of a simple harmonic oscillator is

1
Ev = v + ~ω (82)
2
The energy of ground state (v = 0) of a simple harmonic state is

E0 = 21 ~ω. Thus, we see that the energy of the lowest state (v = 0)
of a simple harmonic oscillator is 21 ~ω and is not zero.
Zero-point energy
The ground state energy of a systems is also called the zero-
point energy. This is the lowest energy a system can have.
This is the energy of the system at absolute zero tempera-
ture. Classically, any system at absolute zero is assumed to
be at absolute rest. All the vibrations or motions in a system
is assumed to cease at absolute zero. However, for quantum
mechanical systems this is not true. Even at absolute zero a
quantum mechanical system fluctuates.
The existence of non-zero zero-point energy is consistent with the

Heisenberg uncertainty principle.
Problem: Using the definition of Uncertainty in linear momen-

tum, show that the lowest energy of a simple harmonic oscillator
is not zero.
Hint: We need to calculate the uncertainty in momentum i.e.
p
for the ground state.
47
Solution: So, let us calculate the required quantities.
Z+∞
hp2x i = ψ0 (x)p̂2x ψ0 (x)dx
−∞
Z+∞r 2 r
α 1 2 2
−2α x d α − 12 α2 x2
= · e −i~ · e dx
π 1/2 dx π 1/2
−∞
Z+∞
α~2 − 21 α2 x2 d
2
− 21 α2 x2
= − 1/2 e e dx
π dx2
−∞
Z+∞
α~2 1 2 2 1 2 2
= − 1/2 e− 2 α x
α 2 α 2 x2 − 1 e− 2 α x
π
−∞
+∞
3 2 Z
α~ 2 2
α2 x2 − 1 e−α x dx

=−
π 1/2
−∞
+∞ +∞
 
α3 ~2
Z Z
2 2 2 2
= − 1/2 α2 x2 e−α x dx − e−α x dx
π
 −∞+∞ −∞
+∞

α3 ~2  2
Z Z
2 2 2 2
= − 1/2 2α x2 e−α x dx − 2 e−α x dx
π
0
3 2
√ √ 0
α~ π π
= − 1/2 2α2 × 3 − 2 ×
π 4α 2α
√
α3 ~2
√
π π
= − 1/2 −
π 2α α
1
= α2 ~2
2
Z+∞
hpx i = ψ0 (x)p̂x ψ0 (x)dx
−∞
Z+∞r r
α 1 2 2
−2α x d α − 21 α2 x2
= · e −i~ · e dx
π 1/2 dx π 1/2
−∞
Z+∞
iα~ 1 2 2 d 1 2 2
= − 1/2 e− 2 α x e− 2 α x dx
π dx
−∞
Z+∞
iα~ 1 2 2 1 2 2
=− e− 2 α x
e− 2 α x
× (−α2 x)dx
π 1/2
−∞
+∞
iα3 ~
Z
2 2
= 1/2 xe−α x
dx
π
−∞
= 0 The integrand is an odd function of x.
48
Thus, uncertainty in momentum
r
p α2 ~2 α~
∆px = hp2x i − hpx i2 = −0= √
2 2
If this is the minimum uncertainty in linear momentum, then the
minimum energy will be
(∆px )2
Emin =
2m
Therefore,
2
(∆px )2 α2 ~2

1 α~
Emin = = √ =
2m 2m 2 4m
Since,
r
mω
α=
~
1
=⇒ Emin = ~ω > 0
4
Thus, the zero-point energy of a simple harmonic oscillator is not
zero.
Heisenberg Uncertainty principle for the simple harmonic oscillato

Let us verify the Heisenberg Uncertainty principle for the ground
state of a particle exhibiting simple harmonic motion. For this, we
need to derive the expression for uncertainty in position in linear
momentum of the particle.
We already know from previous derivation, uncertainty in linear mo-
mentum of a particle exhibiting simple harmonic motion is ∆px =
√1 α~
2
Now, let us calculate the uncertainty in position i.e.
p
Z+∞r r
α − 1 α 2 x2 2 α − 1 α 2 x2
hx2 i = e 2 x e 2 dx
π 1/2 π 1/2
−∞
Z+∞
α 2 2
= 1/2 x2 e−α x dx
π
−∞
Z+∞
2α 2 2
= x2 e−α x
dx
π 1/2
0
2α π 1/2
= 1/2 × Using standard value of the integral
π 4α3
1
= 2
2α
49
Now,
Z+∞r r
α − 1 α 2 x2 α − 1 α 2 x2
hxi = e 2 x e 2 dx
π 1/2 π 1/2
−∞
Z+∞
α 2 2
= 1/2 xe−α x dx
π
−∞
= 0, as the integrand is and odd function of x.
Therefore, uncertainty in position becomes
r
1 1
∆x = − 0 = √
2α2 α 2
Finally, the product of ∆px and ∆x is
1 1 1
∆x∆px = √ α~ × √ = ~
2 α 2 2
Thus, Heisenberg uncertainty principle is valid for a particle exhibit-
ing simple harmonic motion.
Vibrational energy states are equi-spaced
The gap between any two neighboring vibrational levels, say be-
tween v = v and v 0 = v + 1 is given by

0 1 1
∆Ev0 −v = v + ~ω − v + ~ω
2 2

1 1
= v+1+ ~ω − v + ~ω
2 2
= ~ω
Thus, the gap between any two neighboring vibrational states is in-
dependent of the vibrational quantum number of either states. It
depends only upon the frequency of vibration. Thus, the vibrational
energy levels of a simple harmonic oscillator are equi-spaced.
Classical and quantum mechanical turning points:
As discussed previously, during simple harmonic motion, the parti-

cle moves back and forth about the equilibrium position. At equi-
librium position, the kinetic energy is maximum and it gradually
decreases as the particle moves towards the extreme points. At the
extreme points, kinetic energy becomes zero and the total energy
becomes equal to the potential energy. These extreme points are
called turning points (because from this point the particle return
towards the equilibrium position). Thus, the classical turning point
is characterized as a point, where total energy of the system is equal
to its potential energy.
1
At classical turning point: E = kx2ctp
2r
2E
xctp = ±
k
50
Classically, the particle exhibiting simple harmonic motion should
not go beyond this point.
Classical turning point for an electron

Assuming quantum mechanical ground state energy, calculate the
xctp for a simple harmonic oscillator.
q Also assume that the angular
1
frequency of oscillation ω = m (this corresponds to a force con-
stant k = 1 unit).
s
r r r 1/4
~2

2E0 ~ω ~ k
xctp = = = × =
k k k m km
Putting m = 9.1 × 10−31 kg, h = 6.626 × 10−34 J.sec, k = 1 N.m−1 ,
we get xctp = ±3.3257 × 10−10 m.
Classical turning point is not the quantum mechanical turning

point
Let us check the status of the particle beyond xctp , when we treat
it quantum mechanically. To do so, we should check whether the
particle exist or not beyond xctp . That means, we need to evaluate
the wavefunction of our oscillator at some point beyond xctp say, at
xctp + δx (where δx is a very very small but positive distance). Let
us do this for the ground state wavefunction.
r r
α − 1 α2 (xctp +δx)2 α − 12 α2 (x2ctp +2xctp δx+δx2 )
ψ0 (x = xctp + δx) = e 2 = e
π 1/2 π 1/2
r
α h − 1 α2 x2ctp −α2 xctp δx
i
= e 2 ×e ,
π 1/2
(δx2 , being very small is neglected.)
q q
2E0 1
p mω k
Since, xctp = ± k , E0 = 2 ~ω, α = ~ and ω = m we can
write
1 2 2 1 mω 2E0 1 mω ~ω 1 mω 2 1
α xctp = × × = × × = × =
2 2 ~ r k 2 ~ kr 2 k 2
2 mω 2E0 mω ~ω mω 3/2 k
α xctp δx = ± × × δx = ± × × δx = ± √ δx = ± √
~ k ~ k k~ m
Thus,
r
α − 21 k
± √m~ δx
ψ0 (x = xctp + δx) = 1/2
× e × e 6= 0
π
Thus, we see that beyond the classical turning points, the ground
state wavefunction is not zero. In principle, one can verify it for the
other states too. Therefore, the classical turning point is not the
quantum mechanical turning point. The quantum mechanical oscil-
lator goes beyond the classical turning point. This is also called the
tunneling of the quantum mechanical oscillator into classi-
cally forbidden region..
Quantum mechanical turning point: In principle, there is al-

ways a finite probability of finding the particle anywhere between
51
x = +∞ and x = −∞. So, there is no as such quantum mechanical
turning point of the simple harmonic oscillator. This is also obvi-
ous from the expression of wavefunction in ground state. Since, the
wavefunction consist of an exponentially decaying function, it van-
ishes only at x = ±∞. This is another weird example of a quantum
mechanical system. However, for practical purpose we can define
a quantum mechanical turning point by arbitrarily setting a very
small threshold value for the probability density (say, Pth ). Thus,
we can assume that if the probability of finding the particle is less
than Pth then the particle does not go beyond the corresponding
position (xqtp ).
Value of xqtp in ground state:

Let us consider a particle exhibiting a simple harmonic motion be
in its ground state. The quantum mechanical turning point (xqtp )
corresponding to the threshold probability density of Pth can be
obtained from
|ψ0 (xqtp )|2 = Pth
r 2
α − 1 α2 x2qtp
e 2 = Pth
π 1/2
α −α2 x2qtp
e = Pth
π 1/2
Thus s
1 α
xqtp =± ln √ (83)
α Pth π
Example: If an electron q exhibits simple harmonic motion with
1
angular frequency ω = m (this corresponds to a force constant
k = 1 unit) then find xqtp corresponding to the threshold probability
density Pth = 10−6 . Compare this with corresponding xctp .
s r
r m 1/4
mω m 1
α= = × = 2
~ ~ m ~
Thus,
2
1/4 s
m1/4

~
xqtp =± ln √
m Pth ~π
Using m = 9.1 × 10−31 kg, h = 6.626 × 10−34 J.sec, we get, xqtp =

±1.9694 × 10−9 m. The corresponding value of xctp is ±3.3257 ×
10−10 m. Thus xqtp > xctp . That means, quantum mechanical oscil-
lator goes beyond the classical turning point.
Probability of finding the electron beyond the classical limit,

when it is in ground state.
For this, we first need to find a relation between xctp and α for the
ground state.
52
Relationship between xctp and α: for the ground state
s
r r r 2 1/4
2E0 ~ω ~ k ~
xctp = = = × =
k k k m mk
s
r r 1/4
mω m k mk
α= = × =
~ ~ m ~2
1
Thus, xctp = ,
α
=⇒ αxctp = 1
Now, the probability of finding the ground state electron within the
classical limit i.e. within x = +xctp and x = −xctp is given by
+x
Z ctp +x
Z ctpr 2 +x
Z ctp
α − 1 α 2 x2 α 2 2
|ψ0 (x)|2 dx = e 2 dx = 1/2 e−α x
dx
π 1/2 π
−xctp −xctp −xctp
This is a standard definite integral given by

+x
Z ctp
(αxctp )3 (αxctp )5 (αxctp )7

2 2 2
e−α x
dx = αxctp − + − + ...
α 3 10 42
−xctp
Using the relation αxctp = 1, we get

+x
Z ctp
1 2
1 1
|ψ0 (x)|2 dx = 1/2 1 − + − + . . . = 0.8427
π 3 10 42
−xctp
Finally, the probability of finding the ground state electron outside

the classical limit will be 1 − 0.8427 = 0.1573. Thus, in ground
state, there is ≈ 16% chance that the electron will be found in the
classically forbidden region.
Probability of finding the electron beyond the classical limit,

when it is in first excited state.
As before, we first need to find a relation between xctp and α for the
first excited state.
Relationship between xctp and α: for the first excited state

s
r r r 2 1/4
2E1 3~ω 3~ k 9~
xctp = = = × =
k k k m mk
s
r r 1/4
mω m k mk
α= = × =
~ ~ m ~2
√
3
Thus, xctp = ,
√α
=⇒ αxctp = 3
53
Now, the probability of finding the first excited state electron within
the classical limit i.e. within x = +xctp and x = −xctp is given by
+x
Z ctp +x
Z ctp r !2 +x
Z ctp
2α3 − 1 α2 x2 2α 2 2
|ψ1 (x)|2 dx = xe 2 dx = 1/2 α2 x2 e−α x
dx
π 1/2 π
−xctp −xctp −xctp
√
After evaluating the integral and using the relation αxctp = 3 (for
the first excited state), we get
+x
Z ctp
|ψ1 (x)|2 dx = 0.8886
−xctp
Therefore, the probability of finding the particle within the classical

region in first excited state is 0.8886. Therefore, the probability of
finding the electron outside the classical region in first excited state
will be 1 − 0.8886 = 0.1114. Thus, in first excited state, there is
more than 11% chance that the electron will be found in the classi-
cally forbidden region. Note: The probability of finding the particle
in classical region in first excited state (0.8886) is more than that in
ground state (0.8427)
When does a quantum mechanical simple harmonic oscillator

behave as a classical simple harmonic oscillator?
As we have seen above, the probability of finding a simple har-

monic oscillator in the classical region increases on going from the
ground state to the first excited state. This probability will keep
on increasing as one goes to the higher and higher excited states.
That means, as one goes to higher excited state, the simple har-
monic oscillator tends to avoid the classically forbidden region and
tends to stay within the classical region. In other words, the higher
the vibration state of the oscillator the more classically it behaves.
From this, one can easily conclude that for a very large value of v
(vibrational quantum number) the quantum mechanical simple har-
monic oscillator will behave as a classical simple harmonic oscillator.
Why there is a finite probability of finding the oscillator in

classically forbidden region?
You can get a hint of this weird nature from particle in a 1D box
model. We know that in particle in a 1D box, the potential at the
two walls and outside of the 1D box is infinite. However, no such
condition is imposed on a simple harmonic oscillator. Because of
the infinite potential at the two walls and outside of the box, it is
not possible to solve the corresponding Schrödinger equation outside
the box and hence there is no wavefunction of the particle outside
the box.
~2 d2

− + Vout ψout (x) = Eout ψout (x)
2m dx2
~2 d2

− + ∞ ψout (x) = Eout ψout (x), as Vout = ∞
2m dx2
54
That means, the particle does not exist outside the box. But in case
of simple harmonic oscillator, since no such condition is there, the
particle tunnels into the classically forbidden region. If you consider
a finite potential at the two walls and outside the 1D box then also
you can see the tunneling of the particle through the walls of the
box. Tunneling is a very important quantum mechanical phenom-
ena. Many chemical reactions are now know which occurs through
quantum mechanical tunneling effect.
55
Hydrogen atom
So far we have studied the basic principles and concepts in quantum

mechanics and applied those to a very simple model (particle in a box)
and a little bit complex model (simple harmonic oscillator). Now, let us
apply our knowledge of quantum mechanics for studying a real but rel-
atively simpler system – a H-atom in absence of any externally applied
field.
Description of the problem we are going to solve:
A H-atom consists of a positively charged nucleus of mass M and a

negatively charged electron of mass m. The electron is in a state of
continuous motion around the nucleus. In absence of any externally
applied field, the only force the electron experiences is the electrostatic
force of attraction (i.e. Coulombic force)5 due to the nucleus.
e2
Fne =− , (84)
4π0 r2
where q
r = (xe − xn )2 + (ye − yn )2 + (ze − zn )2 (85)
is the distance between the electron and the nucleus and 0 is the per-
mittivity of vacuum. (xe , ye , ze ) and (xn , yn , zn ) are the Cartesian coor-
dinates of the electron and nucleus respectively.
𝑥" , 𝑦" , 𝑧"
𝑟 Nucleus
𝑥& , 𝑦& , 𝑧&
𝑚
Electron
Figure 8: Pictorial representation of H-atom
Our target is to study the H-atom. That means to calculate the energies
and wavefunctions of different quantum mechanical states of H-atom. In
order to do so, we will proceed as before – (A) At first, we will find out the
expression of Hamiltonian for the system, (B) then we’ll set up the cor-
responding Schrödinger equation, and (C) finally solve the Schrödinger
equation.
(A) Hamiltonian for H-atom:
We know, the Hamiltonian consists of kinetic energy and potential en-

ergy operators.
Ĥ = T̂ + V̂ (86)
There are few things to consider here.
(i) Kinetic energy operator (T̂ ) corresponds to the kinetic energy of each
5
The Coulombic force between two charges Q1 and Q2 separated by a distance r is given by
Q1 Q2
FQ1 Q2 =
4π0 r2
56
particle present in the system. Since, H-atom contains one electron and
one nucleus, the kinetic energy operator will be the sum of kinetic energy
operator for the electron (T̂e ) and for the nucleus (T̂n ). Thus,
T̂ = T̂e + T̂n (87)
(ii) Since, a H-atom is a three dimensional system, the kinetic energy

operator of electron and nucleus will be
~2
2
∂2 ∂2 ~2 2

∂
T̂e = − + + =− ∇
2m ∂x2e ∂ye2 ∂ze2 2me e
(88)
~2
2
∂2 ∂2 ~2 2

∂
T̂n = − + + =− ∇ ,
2M ∂x2n ∂yn2 ∂zn2 2mn n
where xe , ye , ze represent the Cartesian coordinates of the electron and
xn , yn , zn are those for the nucleus. m and M are the masses of the
electron and the nucleus respectively. The symbol ∇ is called
‘Nabla’ and
∂ ∂ ∂
is the short form of writing the ‘Del operator’ i.e. ∇ = ∂x + ∂y + ∂z .

2 ∂ ∂ ∂
Similarly, ∇ = ∂x2 + ∂y2 + ∂z 2
(iii) The potential energy of the system can be obtained from Eq. ??.
We know, Fne = − dVdrne . This gives,
e2
V̂ = Vne =− (89)
4π0 r
(iv) Thus, the Hamiltonian of H-atom becomes
~2 2 2
e2
Ĥ = − ∇ e + ∇n − (90)
2me 4π0 r
(v) It is much easier to deal with one-body problem rather than a two-
body problem. Any two-body problem can be simplified to a one-body
problem by introducing the concept of reduced mass (µ) and center of
mass. H-atom system can also be simplified in this way. The reduced
mass of H-atom is given by
mM
µ= .
m+M
By using this, the Hamiltonian (Eq. ??) of H-atom becomes
~2 e2

∂ ∂ ∂
Ĥ = − + + − , (91)
2µ ∂x2 ∂y 2 ∂z 2 4π0 r
where (x, y, z) are given by
x = |xe − xn |
y = |ye − yn |
z = |ze − zn |
The kinetic energy part in H-atom Hamiltonian (Eq. ??) represents the
relative motion of electron and nucleus together.
(B) Schrödinger equation for the H-atom in Cartesian coordinates:
57
If ψn (x, y, z) and En be the wavefunction and energy of nth state in
H-atom then Schrödinger equation can be written as
" #
2 2
~ e
− ∇2 − p ψn (x, y, z) = En ψn (x, y, z),
2µ 4π0 x2 + y 2 + z 2
2 2 2

∂ ∂ ∂
where ∇2 = + +
∂x2 ∂y 2 ∂z 2
(92)
Converting Schrödinger equation in Cartesian coordinates coordinates

to Spherical polar coordinates:6
Why we need this conversion?

The Schrödinger equation (Eq. ??) for H-atom contains three variables
(x, y, z) and hence is a multivariate equation. The first step of solving
this equation involves the application of separation of variable technique.
That means at first we need to break the Eq. ?? into equations contain-
ing only one variable. Without doing this, it is not possible to solve this
equation. But, 2since
the Schrödinger equation containspthe potential
e
energy term 4π 0r
, which contains the term r given by x2 + y 2 + z 2 ,
it is not possible to separate the three variables in this equation. One
way to separate the variables in Eq. ?? is the conversion of the whole
equation in Spherical polar coordinates (r, θ, φ). Since, in spherical po-
lar coordinates the potential energy term is a single variable term, the
problem associated with it is automatically solved. That’s why we first
need to convert the Schrödinger equation (Eq. ??) from Cartesian coor-
dinates to Spherical polar coordinates.
Spherical polar Coordinates and its relation with Cartesian

coordinates:
The Spherical polar coordinates of a point represents the location of
a point on the surface of a sphere (hence the name “spherical”). The
spherical polar coordinates are given by r, θ and φ, where r is the distance
of the point from the center of the sphere (the origin) that means r is
the radius of the sphere, θ is the angle made by the vector ~r with the
z-axis and φ is the angle with x-axis made by the projection of r on xy−
plane.
The relationships between Cartesian coordinates (x, y, z) and Spherical
polar coordinates (r, θ, φ) are given by
x = rsinθcosφ
y = rsinθsinφ (93)
z = rcosθ
Conversion of Schrödinger equation (Eq. ??) to spherical polar

coordinates:
6
Sometimes, people use the name polar Coordinates in place of Spherical polar coordinates. Actually, the term
polar coordinates is used for 2D systems only and hence it has only two variables (r, θ). Spherical polar coordinates
is applicable to 3D systems. Since, in our case, we are dealing with a 3D system we should use the term Spherical
polar coordinates.
58
z
!, #, $
Figure 9: Relation between Spherical polar and Cartesian coordinates
The Schrödinger equation for H-atom is given by Eq. ??. It is obvious

that we just need to convert the ∇2 into Spherical polar coordinates
because the potential energy part is already expressed in terms of r.
Now, for any function f , we can write
∂ 2f ∂ 2f ∂ 2f
2
∇f= + +
∂x2 ∂y 2 ∂z 2
Furthermore,
∂f ∂f ∂r ∂f ∂θ ∂f ∂φ
= + +
∂x ∂r ∂x ∂θ ∂x ∂φ ∂x
∂f ∂f ∂r ∂f ∂θ ∂f ∂φ
= + + (94)
∂y ∂r ∂y ∂θ ∂y ∂φ ∂y
∂f ∂f ∂r ∂f ∂θ ∂f ∂φ
= + +
∂z ∂r ∂z ∂θ ∂z ∂φ ∂z
From Eq. ??, we can write
p z y
r = x2 + y 2 + z 2 , cosθ = p and, tanφ = . (95)
x2 + y 2 + z 2 x
Derivation of x-component of ∇2 f :
From Eq. ??, differentiating r, θ and φ w.r.t. x we get

∂r ∂θ 1 ∂φ sinφ
= sinθcosφ; = cosθcosφ; =− (96)
∂x ∂x r ∂x rsinθ
Putting Eq. ?? into x-component of Eq. ??,
∂f ∂f 1 ∂f sinφ ∂f
= sinθcosφ + cosθcosφ − (97)
∂x ∂r r ∂θ rsinθ ∂φ
Differentiating Eq. ?? w.r.t. x
∂ 2f ∂ 2 f ∂r ∂f ∂φ ∂f ∂θ
= sinθcosφ + sinθ (−sinφ) + cosφ cosθ
∂x2 ∂r2 ∂x ∂r ∂x ∂r ∂x
2
1 ∂ f ∂θ 1 ∂f ∂φ 1 ∂f ∂θ
+ cosθcosφ 2 + cosθ (−sinφ) + cosφ (−sinθ)
r ∂θ ∂x r ∂θ ∂x r ∂θ ∂x
2
∂f 1 ∂r sinφ ∂ f ∂φ 1 ∂f ∂φ
+ cosθcosφ − 2 − − cosφ
∂θ r ∂x rsinθ ∂φ2 ∂x rsinθ ∂φ ∂x

sinφ ∂f cosθ ∂θ sinφ ∂f 1 ∂r
− − 2 − − 2
r ∂φ sin θ ∂x sinθ ∂φ r ∂x
(98)
59
Again, using the expressions from Eq. ??, we get
∂ 2f 2
2
2 ∂ f sin2 φ ∂f cos2 θcos2 φ ∂f cos2 θcos2 φ ∂ 2 f
= sin θcos φ 2 + + +
∂x2 ∂r r ∂r r ∂r r2 ∂θ2
cosθsin2 φ ∂f sinθcosθcos2 φ ∂f sinθcosθcos2 φ ∂f
+ 2 − −
r sinθ ∂θ r2 ∂θ r2 ∂θ
2 2 2
sin φ ∂ f sinφcosφ ∂f cos θsinφcosφ ∂f sinφcosφ ∂f
+ 2 2 + 2 2 + +
r sin θ ∂φ2 r sin θ ∂φ r2 sin2 θ ∂φ r2 ∂φ
(99)
Derivation of y-component of ∇2 f :
From Eq. ??, differentiating r, θ and φ w.r.t. y we get

∂r ∂θ 1 ∂φ cosφ
= sinθsinφ; = cosθsinφ; = (100)
∂y ∂y r ∂y rsinθ
Putting Eq. ?? into y-component of Eq. ??,
∂f ∂f 1 ∂f cosφ ∂f
= sinθsinφ + cosθsinφ + (101)
∂y ∂r r ∂θ rsinθ ∂φ
Differentiating Eq. ?? w.r.t. y
∂ 2f ∂ 2 f ∂r ∂f ∂φ ∂f ∂θ
2
= sinθsinφ 2 + sinθ (cosφ) + sinφ cosθ
∂y ∂r ∂y ∂r ∂y ∂r ∂y
1 ∂ 2 f ∂θ 1 ∂f ∂φ 1 ∂f ∂θ
+ cosθsinφ 2 + cosθ (cosφ) + sinφ (−sinθ)
r ∂θ ∂y r ∂θ ∂y r ∂θ ∂y
2

∂f 1 ∂r cosφ ∂ f ∂φ 1 ∂f ∂φ
+ cosθsinφ − 2 + + (−sinφ)
∂θ r ∂y rsinθ ∂φ2 ∂y rsinθ ∂φ ∂y

cosφ ∂f cosθ ∂θ cosφ ∂f 1 ∂r
+ − 2 + − 2
r ∂φ sin θ ∂y sinθ ∂φ r ∂y
(102)
∂ 2f 2 2 ∂ f
2
cos2 φ ∂f cos2 θsin2 φ ∂f
= sin θsin φ 2 + +
∂y 2 ∂r r ∂r r ∂r
cos2 θsin2 φ ∂ 2 f cosθcos2 φ ∂f sinθcosθsin2 φ ∂f
+ + −
r2 ∂θ2 r2 sinθ ∂θ r2 ∂θ (103)
2 2 2
sinθcosθsin φ ∂f cos φ ∂ f sinφcosφ ∂f
− + − 2 2
r2 ∂θ r2 sin2 θ ∂φ2 r sin θ ∂φ
2
cos θsinφcosφ ∂f sinφcosφ ∂f
− −
r2 sin2 θ ∂φ r2 ∂φ
∂ 2f 2 2 ∂ f
2
cos2 φ ∂f cos2 θsin2 φ ∂f cos2 θsin2 φ ∂ 2 f
= sin θsin φ 2 + + +
∂y 2 ∂r r ∂r r ∂r r2 ∂θ2
cosθcos2 φ ∂f 2sinθcosθsin2 φ ∂f cos2 φ ∂ 2 f sinφcosφ ∂f
+ − + − 2 2
r2 sinθ ∂θ r2 ∂θ r2 sin2 θ ∂φ2 r sin θ ∂φ
2
cos θsinφcosφ ∂f sinφcosφ ∂f
− −
r2 sin2 θ ∂φ r2 ∂φ
(104)
60
Derivation of z-component of ∇2 f :
From Eq. ??, differentiating r, θ and φ w.r.t. z we get
∂r ∂θ sinθ ∂φ
= cosθ; =− ; =0 (105)
∂z ∂z r ∂z
Putting Eq. ?? into z-component of Eq. ??,
∂f ∂f sinθ ∂f
= cosθ − (106)
∂z ∂r r ∂θ
Differentiating Eq. ?? w.r.t. z
∂ 2f ∂ 2 f ∂r ∂f ∂θ sinθ ∂ 2 f ∂θ 1 ∂f ∂θ
= cosθ − sinθ − − cosθ
∂z 2 ∂r2∂z ∂r ∂z r ∂θ2 ∂z r ∂θ ∂z
(107)
∂f 1 ∂r
− sinθ − 2
∂θ r ∂z
∂ 2f 2
2 ∂ f sin2 θ ∂f sin2 θ ∂ 2 f sinθcosθ ∂f sinθcosθ ∂f
= cos θ 2 + + 2 + +
∂z 2 ∂r r ∂r r ∂θ2 r2 ∂θ r2 ∂θ
(108)
∂ 2f 2
2 ∂ f sin2 θ ∂f sin2 θ ∂ 2 f 2sinθcosθ ∂f
= cos θ 2 + + 2 + (109)
∂z 2 ∂r r ∂r r ∂θ2 r2 ∂θ
Final expression of ∇2 in Spherical polar coordinates:
Adding Eqs. ??, ?? and ??, we get
2∂ 2 f 2 ∂f 1 ∂ 2f cosθ ∂f 1 ∂ 2f
∇f= 2 + + + + (110)
∂r r ∂r r2 ∂θ2 r2 sinθ ∂θ r2 sin2 θ ∂φ2
which can be written in the final form as
∂2

1 ∂ ∂ 1 ∂ ∂ 1
∇2 = 2 r2 + 2 sinθ + (111)
r ∂r ∂r r sinθ ∂θ ∂θ r2 sin2 θ ∂φ2
Hamiltonian and Schrödinger equation for H-atom, in Spherical

polar coordinates:
From Eqs. ?? and ??, we can write down the Hamiltonian for H-atom
in Spherical polar coordinates.
2
∂2 e2

~ 1 ∂ 2 ∂ 1 ∂ ∂ 1
Ĥ = − r + 2 sinθ + 2 2 −
2µ r2 ∂r ∂r r sinθ ∂θ ∂θ r sin θ ∂φ2 4π0 r
and
Ĥψn (r, θ, φ) = En ψn (r, θ, φ) (112)
61
Note that the wavefunction is now written with variables (r, θ, φ).
Separation of variable technique:
As mentioned before, the main reason of converting the Schrödinger

equation for H-atom in Spherical polar coordinates is to make it suitable
for separating the variables in it, so that we can solve it. An equation
containing only one variable is easy to solve than an equation contain-
ing many variables. Separation of variables is a technique by which one
can break a multivariate equation into simple equations containing only
one variable. Eq. ?? has three variables (r, θ, φ) so, our next step is to
separate these three variables and obtain three different equations in r, θ
and φ separately. Before we proceed, let us have a brief description of
steps involved in separation of variable technique.
Steps involved in separation of variable technique:
The general steps involved in separation of variable technique are –
(i) Write down the solution of the equation as a product of

functions of only one variable. A more in-depth discussion on it
is given later on. In particular, how the emergence of quantum number
is related to it. Anyway, in this step, The wavefunction is written as a
product of three functions each depending on one and only one coordi-
nate i.e. ψ(r, θ, φ) = R(r) × Θ(θ) × Φ(φ).
(ii) Rearrange the main equation in such a way that the left and
right hand sides of the equation depends only one one variable.
In Cartesian coordinates, the Eq. ?? cannot be written in this way be-
cause of the potential energy term that contains √ 2 1 2 2 . However,
x +y +z
we can do this with Eq. ??.
(iii) If Step (ii) is finished successfully, one can write each side
of the equation as a constant. This is because each side depends only
on one variable and thus two different quantities depending on two dif-
ferent things will be equal if and only if both equals to the same constant.
Applying separation of variable technique on Eq. ??
Since there are three variables in Eq. ??, we will separate the variables
in two steps.
(A) At first we will separate the radial part (R(r), which depends only
on r) and the angular part (Y (θ, φ), which depends one θ and φ).
(B) Then we will separate the θ and the φ parts from Y (θ, φ).
(A) Separation of radial (r) and angular (θ, φ) parts of Eq. ??
We will follow the three steps of separation of variable technique (as

described above). But before that let us first rewrite the Eq. ?? in a
more convenient way. Thus,
62
2
2
1 ∂ ∂ψ n 1 ∂ ∂ψ n 1 ∂ ψ n 2µ e
r2 + 2 sinθ + 2 2 + + En ψn = 0
r2 ∂r ∂r r sinθ ∂θ ∂θ r sin θ ∂φ2 ~2 4π0 r
(113)
Note, in the the above equation, for clarity we have omitted the vari-
ables in ψ.
Step (i): Write down the solution of the equation as a product

of functions of only one variable.
We can write the wavefunction ψ(r, θ, φ) as a product of two functions –

one depending only on r (R(r)) and the other (Y (θ, φ)) depending one
θ and φ.
ψ(r, θ, φ) = R(r) × Y (θ, φ)
(114)
or, ψ = R × Y
Step (ii): Write down the Eq ?? in such a way that the left and
Putting Eq. ?? in Eq. ??.

1 ∂ 2 RY
2
1 ∂ 2 ∂RY 1 ∂ ∂RY 2µ e
r + 2 sinθ + 2 2 + 2 + E RY
r2 ∂r ∂r r sinθ ∂θ ∂θ r sin θ ∂φ2 ~ 4π0 r
Since R depends only on r and Y depends only on (θ, φ), we can write
2
2
Y ∂ ∂R R ∂ ∂Y R ∂ Y 2µ e
2
r2 + 2 sinθ + 2 2 + + E RY = 0
r ∂r ∂r r sinθ ∂θ ∂θ r sin θ ∂φ2 ~2 4π0 r
2
r
Multiplying both sides by RY , we get
1 ∂ 2 Y 2µr2
2
1 ∂ 2 ∂R 1 ∂ ∂Y e
r + sinθ + + 2 +E =0
R ∂r ∂r Y sinθ ∂θ ∂θ Y sin2 θ ∂φ2 ~ 4π0 r
Writing all the r-dependent parts on left hand side and Y -dependent
parts on the right hand side.
2
2
1 ∂ 2Y

1 ∂ ∂R 2µr e 1 ∂ ∂Y
r2 + 2 +E =− sinθ −
R ∂r ∂r ~ 4π0 r Y sinθ ∂θ ∂θ Y sin2 θ ∂φ2
(115)
Step (iii): Write each side of the Eq. ?? as a constant.
Since left hand side of this equation depends only on r and the right hand
side depends only on angles (θ, φ), each should be equal to a constant
(say, A). Thus, the radial part of Schrödinger equation for H-atom is
2µr2
2
1 d 2 dR e
r + 2 +E =A
R dr dr ~ 4π0 r
or,
2µr2 e2

d dR
r2 + 2 + E R − AR = 0. (116)
dr dr ~ 4π0 r
63
Note the change of partial derivative to full derivative in Eq. ??. This
is because there is only one variable in this equation.
(B) Separating the θ and the φ parts:
The angular part of Schrödinger equation for H-atom is
1 ∂ 2Y

1 ∂ ∂Y
− sinθ − =A
Y sinθ ∂θ ∂θ Y sin2 θ ∂φ2
or,
1 ∂ 2Y

1 ∂ ∂Y
sinθ + + AY = 0 (117)
sinθ ∂θ ∂θ sin2 θ ∂φ2
Note: Here we still use the partial derivatives, because it contains two
variables θ and φ.
Separating the polar (θ) and azimuthal (φ) parts of Eq. ??
For separating the polar and azimuthal parts of Eq. ??, we will proceed
in the same way, as before.
Step (i): Write down the solution of the Eq. ?? as a product of

functions of only one variable.
The solution of Eq. ?? can be written as
Y (θ, φ) = Θ(θ) × Φ(φ)

(118)
or, Y = ΘΦ
Step (ii): Write down the Eq. ?? in such a way that the left and
Putting Eq. ?? in Eq. ??,
1 ∂ 2 ΘΦ

1 ∂ ∂ΘΦ
sinθ + + AΘΦ = 0
Since Θ depends only on θ and Φ depends only on φ, we can write
Θ ∂ 2Φ

Φ ∂ ∂Θ
sinθ + + AΘΦ = 0
2
Multiplying both sides by sin θ
ΘΦ ,
1 ∂ 2Φ

sinθ ∂ ∂Θ
sinθ + 2
+ Asin2 θ = 0
Θ ∂θ ∂θ Φ ∂φ
(119)
1 ∂ 2Φ

sinθ ∂ ∂Θ 2
sinθ + Asin θ = −
Θ ∂θ ∂θ Φ ∂φ2
Step (iii): Write each side of the Eq. ?? as a constant.
64
As before, since left hand side of Eq. ?? depends only on θ and right
hand side depends only on φ, we can write each of them equal to a
constant (say, B). Thus, the polar part of Schrödinger equation is

sinθ d dΘ
sinθ + Asin2 θ = B
Θ dθ dθ
or

d dΘ
+ Asin2 θ − B Θ = 0

sinθ sinθ (120)
dθ dθ
and the azimuthal part of Schrödinger equation is
1 d2 Φ
− =B
Φ dφ2
or,
d2 Φ
+ BΦ = 0 (121)
dφ2
Solving the azimuthal equation (Eq. ??) of H-atom
The azimuthal equation (Eq. ??) is a standard second order differential

equation. It has a general solution of
Φ = ceimφ , (122)
where m = B 1/2 . φ is called the azimuthal angle and its values can vary
from 0 to 2π. It is obvious from Fig. ?? that after tracing an angle of
2π we reach at the same point. Thus, the value of Φ should also be the
same at φ = 0 and φ = 2π. Therefore,
Φ(φ = 0) = Φ(φ = 2π)

c = ce2imπ
e2imπ = 1
cos2mπ + isin2mπ = 1, Using, eix = cosx + isinx
Since the right hand side is a real number and left hand side is a complex
quantity, the equality will be satisfied if and only if the imaginary part
equals zero i.e.
sin2mπ = 0
This is possible if and only if m be a positive or negative integer including
zero. Thus,
m = 0, ±1, ±2, ±3, . . .
m is called the magnetic quantum number.
Determining the normalization constant c in Eq. ??:
65
c in the azimuthal wavefunction (Eq. ??) can be determined by applying
the condition of normalization. Thus,
Z2π
Φ∗ Φdφ = 1
0
Z2π
c2 e−2imφ e2imφ dφ = 1
0
Z2π
c2 dφ = 1
0
2
c × 2π = 1
1
c= √
2π
Thus, the azimuthal wavefunction becomes
1
Φm = √ eimφ (123)
2π
The subscript m is added to represent the dependence of Φ on m.
Solution of the θ-part or polar equation i.e. Eq. ?? of H-atom
The general solution of Eq. ?? is the associated Legendre’s polynomial

(Plm (cosθ)), given by
For positive m:
∞ ∞
" #
X c2k X c2k+1
Plm>0 (cosθ) = sinm θ c0 cos2k θ + c1 cos2k+1 θ ,
c0 c1
k=0 k=1
(124)
(k + m)(k + m + 1) − A
where ck+2 = ck , and A = l(l + 1)
(k + 1)(k + 2))
For negative m:
(l − |m|)! m>0
Plm<0 (cosθ) = (−1)|m| P (cosθ) (125)
(l + |m|)! l
Thus, the normalized solution of Eq. ?? is
Θl,m = Nl,m Plm (cosθ), Nl,m = Normalization constant (126)
The subscripts l and m are added to show the dependence of Θ on these

two quantities. l is an integer and is called azimuthal quantum num-
ber. The value of l controls the value of magnetic quantum number,
m. For each value of l there are 2l + 1 allowed values of m given by
−l, −(l − 1), . . . , 0, . . . , (l − 1), l. The restrictions on the values of l and
m is for ensuring the convergence of the series in Eq. ??. The values of
c0 and c1 are also chosen for each set of (l, m) in such a way that the
66
convergence of the series is ensured.
The expression of Plm (cosθ) for some selected sets of (l, m) are –
l ↓, m → -2 -1 0 1 2
0 - - 1 - -
1
1 - 2 sinθ cosθ −sinθ -
2
1 1 1
3cos θ − 1 −3sinθcosθ 3sin2 θ
2

2 8 sin θ 2 sinθcosθ 2
Solution of the radial equation i.e. Eq. ?? of H-atom
The general solution of radial equation (Eq. ??) of H-atom is given by
∞
l X k
2r 2r r
Rn,l (r) = ck e− na0
na0 na0
k=0 (127)
k+l+1−n
where, ck+1 = ck
(k + 1)(k + 2l + 2)
In Eq. ??
µαc e2
a0 = and α = (128)
~ 4π0 ~c
µ = reduced mass, α is called fine structure constant, c = speed of light
h
in vacuum and ~ = 2π is called reduced Planck’s constant, e = charge of
an electron and 0 = permittivity of vacuum. All these quantities are in
SI unit and are constants. Therefore, a0 is also a constant. It is called
Bohr’s radius and it’s value is 0.529177Å.
n in Eq. ?? is a positive integer (6= 0) and is called Principal quantum

number. The value of n controls the value of azimuthal quantum num-
ber l. For each n, l has values from 0 to (n − 1). This restriction on
the values of l is imposed for ensuring convergence of the series in Eq. ??
Energy expressions
The solution of radial part also gives the expression for energy (En )7 .
µe4
En = − 2 2 2 (129)
80 n h
Why there are quantum number?
The Step (i) of separation of variable technique involves the writing of

the wavefunction as a product of three functions, each depending on one
variable only. As such it is not a simple task. We cannot always write
any multivariate function as a product of one-variable functions. How-
ever, we know that a function can be written as a series expansion. This
property can be used to express a multivariate function as a product of
single-variable functions. Suppose, there be a function f (r, θ) = sin(rθ).
7
This is the energy appeared in Schrödinger equation: Ĥψn = En ψn (See, Eq. ??)
67
How can you write this function as f (r, θ) = g(r)h(θ)? It’s a difficult
task. However, if you write, sin(rθ) as a series expansion, then it be-
comes simple. Thus,
∞
(rθ)3 (rθ)5 X (rθ)2k+1 X
sin(rθ) = rθ − + −··· = (−1)k = gk (r)hk (θ)
3! 5! (2k + 1)!
k=0 k
(130)
Thus, we see that although it may not be possible to write a multivari-
ate function as a product of single variable functions yet it is possible to
write the same as a sum of products of single-variable functions. Note
that the example given above is a simple case because we knew the
function. In case of Schrödinger equation, we do not know the form of
the wavefunction (ψ(r, θ, φ)), but still we expressed it as a product of
R(r), Θ(θ) and Φ(φ). That’s why, later on when one solves the indi-
vidual equations (Eqs. ??, ?? and ??), one gets the solutions as series
expansions. Since these series represent the part of wavefunctions i.e. a
real system, it must converge to satisfy the real situations and boundary
conditions. This requirement of convergence of the series puts restric-
tions on different quantities like A and B in Eqs. ?? and ??. These
restrictions emerges in the form of quantum numbers. There is one
equation corresponding to each variable in the wavefunction and each
equation gives rise to one quantum number. That’s why there are three
quantum numbers.
But we know four quantum numbers!
Yes, that’s true. There is the fourth quantum number – spin quantum
number. It emerges when one considers the relativistic effect. Since
the electrons in an atom moves with a speed comparable to the speed
of light one should always consider relativistic effect in the description
of electronic structure. Relativistic effect is out of the scope of this book.
Summary important points to remember:

• Three quantum numbers are appeared from the solution of Schrödinger
equation for H-atom.
• Principal quantum number (n) is obtained from the solution of ra-
dial (r) part. It is always a positive integer (6= 0). Thus, n =
1, 2, 3, . . .
• Azimuthal quantum number (l) is obtained from the solution of
polar (θ) part. Its value is controlled by the value of n. For each n,
l = 0, 1, 2, . . . , (n − 1).
• Magnetic quantum number (m) is obtained from the solution of
azimuthal (φ) part. Its value is controlled by the value of l. For
each l, m = −l, −(l − 1), . . . , 0, . . . , (l − 1), l.
• The conditions on the values of n, l and m comes directly from the
solution of the equations. For example,
– n should always be a positive integer. A negative integer value
of n is not allowed as this will make the radial wavefunction
Rn,l (Eq. ??) exponentially increasing and thus at r = ∞ the
wavefunction will become ∞, which is not allowed. Similarly,
n = 0 will also make Rn,l = ∞ for any value of r.
68
– The value of l is controlled by the value of n in such a way that
the recursion series in Eq. ?? is converged.
– The value of m is controlled by the value of l for the same reason
i.e. to allow the recursion series in Eq. ?? to converge. The
allowed values of m as positive or negative integers including
zero is already discussed while solving the azimuthal equation.
• Thus, each quantum mechanical state is characterized by these three
quantum numbers (nlm).
• There is a fourth quantum number called spin quantum number,
which arises due to relativistic effect and it takes the values of ± 12
for each value of m.
• The first state or the ground state of H-atom is characterized by
n = 1, l = 0, m = 0 or simply (100). Since, n = 1 allows only one
value of l i.e. l = 0, which in turn allows only one value of m i.e.
m = 0, the ground state has a degeneracy level of 1. That means,
the ground state is non-degenerate.
• For the first excited state, n = 2, which allows two values of l i.e.
l = 0, 1. Now, l = 0 allows only one value of m i.e. m = 0 and l = 1
allows three values of m i.e. m = −1, 0, +1. Thus, the first excited
state is four fold degenerate, as shown below
n l m n, l, m
1 0 0 1, 0, 0
2 0 0 2, 0, 0
2 1 -1 2, 1, −1
2 1 0 2, 1, 0
2 1 1 2, 1, 1
• Thus, degeneracy of ground state = 1, degeneracy of first excited

state = 4. In general, any state designated by the Principal quantum
number n has a degenearcy of = n2 .
• The dependence of energy (Eq. ??) on n2 also reflects the level of
degeneracy of the state.
• Since energy (E) appeared only in the radial part of Schrödinger
equation, it depends only on the principal quantum number. How-
ever, inherently it takes into account the number of values of l and
m also.
• Since the energy depends only on n, the states are primarily desig-
nated by the value of n. Thus, n = 1 is called K-shell (which is the
ground state), n = 2 is L-shell, n = 3 is M-shell and so on.
• Since each value of n corresponds to a range of l values, each value
of l is called a sub-shell. Thus l = 0 is called s-subshell, l = 1 is
p-subshell, l = 2 is d-subshell, l = 3 is f-subshell and so on.
• Furthermore, since each value of l corresponds to (2l + 1) number of
m values, each subshell is further divided into (2l + 1) number of or-
bitals. Thus, each s-subshell contains 1 orbital, each p-subshell con-
tains 3 orbitals, each d-subshell contains 5 orbitals, each f -subshell
contains 7 orbitals and so on.
• The orbitals within a subshell are further named according to their
m values and/or structural features. For example, the three p-
orbitals can be named as p+1 , p0 and p−1 . Later on, we’ll see that
69
the p-orbital are actually named as px , py and pz . Similarly, the five
d-orbitals are named as dxy , dxxz , dyz , dx2 −y2 and dz 2 .
• Since there is only one orbital in a s-shell, it is not given separate
name. Thus, the names s-subshell and s-orbital are synonymous.
Origin of orbital’s name
The names s, p, d, f, g, . . . are derived from spectroscopic terms. s
stands for sharp, p for principal, d for diffuse and f for funda-
mental. These names (sharp, principal, diffuse, fundamental ) were
originated long before quantum mechanics was developed. When
the electronic structure was not known to the researchers they clas-
sified the spectral lines according to their pattern in the spectra.
Later on, when the idea of quantum numbers become clear the
name of the orbitals were given on the basis of the corresponding
pattern of the spectral lines associated with those orbitals.
The expression of radial (Rnl ) and angular (Y (θ, φ) = Θl,m × Φm )

parts and total wavefunctions (ψnlm ) for the first two states in
H-atom
Note that the radial and angular parts and hence the total wavefunctions
given in Table ?? are not normalized. We’ll consider the normalization
in the next section.
Table 1: Radial, angular and total wavefunctions of first two states in H-atom
n l m Rn,l Y (θ, φ) ψnlm Name
R −r/a0
1 0 0 N10 e A
N00 N100 e−r/a0 1s
R r −r/2a0 A r −r/2a0
2 0 0 N20 (2 − a0 )e N00 N200 (2 − a0 )e 2s
R −r/2a0
2 1 0 N21 re A
N10 cosθ N210 re−r/2a0 cosθ 2p
R −r/2a0
2 1 +1 N21 re A
−N11 sinθe±iφ −N211 re−r/2a0 sinθe±iφ 2p
R −r/2a0
2 1 −1 N21 re A
N11 sinθe±iφ N211 re−r/2a0 sinθe±iφ 2p
The normalization constants for the radial, angular and to-

R A
tal wavefunctions are represented respectively by Nnl , Nlm
and Nnlm (= NnlR
× NlmA
). Note: in last row, the factor 12
in angular part is absorbed into the normalization constant.
Normalization of Rn,l and Y (θ, φ) = Yl,m (θ, φ) for the first two
states of H-atom:
Before we proceed, let us discuss a little bit about normalization in

Spherical polar coordinates. The normalization of a wavefunction (say,
ψ(r, θ, φ)) requires to solve the following equation to find the value of
the normalization constant N .
70
Z θmax φ
rmax Z Zmax
N 2 ψ ∗ (r, θ, φ)ψ(r, θ, φ)dτ = 1,
rmin θmin φmin
where (rmin , θmin , φmin ) and (rmax , θmax , φmax ) are respectively the lower
and upper limits of (r, θ, φ). The integration should be carried over all
the variables present in the wavefunction taking into account the proper
limits and the volume element (dτ ). The limits of r, θ and φ are
rmin , rmax ≡ 0, ∞
θmin , θmax ≡ 0, π
φmin , φmax ≡ 0, 2π
Care should be taken to consider the volume element dτ . In Cartesian

coordinates, the volume element is simply dxdydz.
dτ in Cartesian coordinates: dxdydz
But in Spherical polar coordinates it is not that simple.
dτ in Spherical polar coordinates: r2 sinθdrdθdφ
This expression for volume element in Spherical polar coordinates is de-

rived in Appendix.
Thus, to normalize different parts of wavefunctions, we need to

solve the following equations
Z∞
∗
r part only: Rn,l Rn,l r2 dr = 1 (131)
0
Zπ
θ part only: Θ∗l,m Θl,m sinθdθ = 1 (132)
0
Z2π
φ part only: Φ∗m Φm dφ = 1 (133)
0
Zπ Z2π
∗
Yl,m i.e. Angular part: Yl,m Yl,m sinθ dθ dφ = 1 (134)
0 0
Z∞ Zπ Z2π
∗
whole wavefunction: ψn,l,m ψn,l,m r2 sinθdrdθdφ = 1
0 0 0
(135)
Now we can proceed to normalize the different parts of the wavefunc-

tions.
71
Normalizing R1,0
Z∞
∗ R −r/a0
R1,0 R1,0 r2 dr = 1 R1,0 = N10 e
0
Z∞
2
R
N10 e−2r/a0 × r2 dr = 1
0 (136)
Z∞
2
R
N10 r2 e−2r/a0 dr = 1
0
R 2
a30 R 2
N10 × = 1 =⇒ N10 = 3/2
4 a0
Normalizing Y0,0
Zπ Z2π
∗ A
Y0,0 Y0,0 sinθdθdφ = 1 Y0,0 = N00
0 0
Z Z2π
π
A
2
N00 sinθdθdφ = 1
0 0 (137)
Zπ Z2π
A 2

N00 sinθdθ dφ = 1
0 0
A
2 A 1
N00 × 2 × 2π = 1 =⇒ N00 = √
2 π
Combining the above two normalization constant, we get
1
N100 = p 3 . (138)
πa0
Thus, the complete expression of ground state wavefunction becomes
1
ψ100 = p 3 e−r/a0 . (139)
πa0
Normalizing R2,0
Z∞
∗ r
R2,0 R2,0 r2 dr = 1, R
R2,0 = N2,0 2− e−r/2a0
a0
0
Z∞ 2
R 2 r
e−r/a0 × r2 dr = 1

N20 2−
a0
0
 ∞
Z∞ Z∞

Z
R 2

2 −r/a0 4 3 −r/a0 1 4 −r/a0

N20 4 r e dr − r e dr + 2 r e dr = 1
 a0 a0 
0 0 0

R 2 4 1 1
4 × 2a30 − × 6a40 + 2 × 24a50 = 1 =⇒ N20 R

N20 =p 3
a0 a0 8a0
(140)
72
Since the wavefunction of first excited state ψ200 contains the same an-
gular part (Y00 ) as the ground state, we can write the total wavefunction
of first excited state of H-atom as

1 r
ψ200 = p 3
2− e−r/2a0 (141)
32πa0 a0
Normalizing R2,1
Z∞
∗
R2,1 R2,1 r2 dr = 1, R
R2,1 = N2,1 re−r/2a0
0
Z∞
2
R
N21 r2 e−r/a0 × r2 dr = 1
0 (142)
Z∞
2
R
N21 r4 e−r/a0 dr = 1
0
R
2 1
N21 × 24a50 = 1 =⇒ N21
R
=p 5
24a0
Normalizing Y1,0
Zπ Z2π
∗ A
Y1,0 Y1,0 sinθdθdφ = 1 Y1,0 = N10 cosθ
0 0
Z Z2π
π
A
2
N10 cos2 θsinθdθdφ = 1
0 0 (143)
Zπ Z2π
A
2
N10 cos2 θsinθdθ dφ = 1
0 0
r
A 2
2 A 3
N10 × × 2π = 1 =⇒ N10 =
3 4π
Combining the normalization constants for Y10 and R2,1 , the total wave-
funciton of the (2, 1, 0) state of H-atom becomes
1
ψ210 = p 5
r cosθ e−r/2a0 (144)
32πa0
73
Normalizing Y1,±1
Zπ Z2π
∗
Y1,±1 Y1,±1 sinθdθdφ = 1 A
Y1,±1 = ∓N11 sinθe±iφ
0 0
Z Z2π
π
2
A
N11 sin2 θe∓iφ e±iφ sinθdθdφ = 1
0 0 (145)
Zπ Z2π
A
2
N11 sin3 θdθ dφ = 1
0 0
r
A 2
4 A 3
N11 × × 2π = 1 =⇒ N11 =
3 8π
Thus, the (211) wavefunction becomes
1

±iφ− 2ar
ψ2,1,±1 = ∓ p r sinθ e 0 (146)
64πa50
Radial and angular distribution:
From the probabilistic interpretation of wavefunction, we know that the

ψ(r, θ, φ)ψ ∗ (r, θ, φ) represents the probability density of the electron at
point (r, θ, φ). When we multiply this probability density with a vol-
ume element dτ , then ψ(r, θ, φ)ψ ∗ (r, θ, φ)dτ becomes the probability of
finding the particle in a small sphere around the point (r, θ, φ). Note:
We set the sum of all such probabilities within all space i.e. the total
probability to 1 for normalizing the wavefunction. Thus, if P (r, θ, φ) be
the probability density at the point (r, θ, φ), we can write
P (r, θ, φ)dτ = ψ(r, θ, φ)ψ ∗ (r, θ, φ) r2 sinθ dr dθ dφ (147)
Since the wavefunction has two parts – radial and angular, there exist
both the radial and angular distributions. Thus, the radial and angular
probability densities are given as
∗
P (r) = Rn,l Rn,l
∗ (148)
P (θ, φ) = Yl,m Yl,m
∗
The quantity 4πr2 Rn,l Rn,l is called radial distribution function. It
describes the probability of finding the electron in a small volume ele-
ment between r and r + dr in all directions in an orbital. Note: since
there is no directional preference, the volume element simply becomes
4πr2 (see the footnote 8 ). The angular probability density describes the
shape of the space around the nucleus where the probability of finding
the electron is maximum. That means, it describes the shape of the
orbitals.
8
If τ be the volume of a sphere, then
4 2
τ= πr =⇒ dτ = 4πr2 dr
3
74
Plot of radial distribution function in H-atom
Spherical harmonics, concept of orbitals, Real and imaginary

wavefunctions and shape of the orbitals:
Spherical Harmonics:
The solutions of angular part of the wavefunctions i.e. Ylm (θ, φ) are
called spherical harmonics. Spherical harmonics are basically some spe-
cial functions described on the surface of a sphere. Why sphere? Be-
cause, θ and φ are two spherical polar coordinates and spherical polar
coordinates represent the location of a point on a sphere. Later on, you’ll
see how can one obtain the shape of different orbitals from the spherical
harmonics.
In an atom, the spherical harmonics describe the shape of the space

where the electrons can move. That means spherical harmonics describe
the shape of different orbitals. Since, for any s-orbital (l = 0), the
spherical harmonics is a constant (Y00 = 2√1 π ), it indicates a spherically
symmetrical shape. Thus, an s-orbital is spherical in shape.
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Figure 10: visualizing s-orbital
You can plot the spherical harmonics to visualize it (as in Fig. ??).
This can be done by many softwares. In Appendix is given a step by step
method of how to plot spherical harmonics using GNUPLOT (a free soft-
ware).
For any p-subshell (l = 1), there are three spherical harmonics corre-
sponding to three p-orbitals. The spherical
q harmonics of a p-orbital with
3
m = 0 is a real function (Eq. ??, Y10 = 4π cosθ). This is called pz or-
bital. The name comes from the functional form (Remember, z = rcosθ
in Eq. ??). When the spherical harmonics is plotted, it looks like a
dumb-bell with the lobes along the z-axis. This justifies the nomencla-
ture of l = 1, m = 0 orbital as pz .
The other two p-orbitals corresponding to m = ±1 have complex spher-
ical harmonics (Eq. ??). These orbitals can be termed as p+1 and p−1 .
2.1.1. energy expressions (without derivation), degeneracy
2.1.2. Hydrogenic wave functions up to n = 2 (expression only)
75
Figure 11: visualizing pz -orbital
2.1.3. real wavefunction

2.1.4. concept of orbials and shapes of s and p orbitals
76
3. University questions:
2
2017: 1) Verify that the wavefunction Ae−Bx /2 is an eigenfunction of the p simple
harmonic oscillator (in one dimension) Hamiltonian. Here B = 2π (mk)/h
(terms have their usual significance). Find the expression for the eigenvalue.
Solution: The Hamiltonian for a simple harmonic oscillator is given by
h2 d2 1 2
Ĥ = − 2 + kx ,
8π m dx2 2
where k is the force constant. Let us apply this hamiltonian on the given
2
wavefunction Ψ(x) = Ae−Bx /2 .
h2 d2 Ψ(x) 1 2
ĤΨ(x) = − 2 + kx Ψ(x)
8π m dx2 2
2 2
h d −Bx2 /2 1 2 −Bx2 /2
= −A 2 e + kx Ae
8π m dx2 2
2
h d n
−Bx2 /2
o 1 2
= −A 2 −Bxe + kx2 Ae−Bx /2
8π m dx 2
2 n
h −Bx2 /2

−Bx2 /2
o 1 2
= AB 2 x −Bxe +e + kx2 Ae−Bx /2
8π m 2
2 2
h 2 h 2 1 2
= −AB 2 2 x2 e−Bx /2 + AB 2 e−Bx /2 + kx2 Ae−Bx /2
8π m 8π m 2
p
Since B = 2π (mk)/h =⇒ B 2 = 4π 2 mk/h2 . Putting these in the above
equation,
√
h2 4π 2 mk 2 −Bx2 /2 2π mk h2 −Bx2 /2 1 2 −Bx2 /2
ĤΨ(x) = −A 2 xe +A e + kx Ae
8π m h2 r h 8π 2m 2
1 2 h k −Bx2 /2 1 2 −Bx2 /2
= −A kx2 e−Bx /2 + A e + kx Ae
r2 4π m 2
h k −Bx2 /2
= Ae
4π m r
1 2 k
= ~ωAe−Bx /2 , where, ω = = angular frequency of oscillation.
2 m
Thus, the given wavefunction is an eigenfunction of a one-dimensional q simple
harmonic oscillator. The corresponding eigenvalue is 21 ~ω, where ω = mk .
2) From the eigenvalue obtained above, make an estimate of the positions of
the Classical Turning points x1 and x2 i.e. values of x after which the motion
reverses its direction. Use proper arguments.
Solution: The classical turning point is the point, where the kinetic energy
of the simple harmonic oscillator becomes zero and the whole energy (i.e. the
eigenvalue obtained above) becomes equal to the potential energy (i.e. 12 kx2 ).
So, at classical turning point,
1 1
~ω = kx2
2 2r
~ω
x=±
k
Thus,
r
~ω
x1 = +
rk
~ω
x2 = −
k
77
3/2
3) The 1s wavefunction for the H-atom is Ψ = 1 √1
e−r/a0 , where a0 is
a0 π
the Bohr radius. Calculate the probability of finding the electron within a
distance a0 from the nucleus. Given
Z∞
n!
xn e−bx dx = ; (n > −1)
bn+1
0
Solution: The probability of finding a particle (having wavefunction Ψ(r))

between the two points r = r1 and r = r2 is given by
Zr2
P = Ψ∗ (r)Ψ(r) × 4πr2 dr
r1
3/2
In our case, Ψ(r) = 1 √1
e−r/a0 and r1 = 0, r2 = a0 . Therefore, the
a0 π
probability of finding the electron within the Bohr radius is
Za0 3/2 3/2
1 1 −r/a0 1 1
P = √ e ×√ e−r/a0 × 4πr2 dr
π a0 π a0
0
Za0
4
= 3 r2 e−2r/a0 dr
a0
Z 0 Z Z a0
4 2 d
= 3 r e−2r/a0 dr − r2 e−2r/a0 dr dr
a0 dr
Z a0 0
4 a0 a0
= 3 r2 − e−2r/a0 − 2r − e−2r/a0 dr
a0 2 2 0
Z a0
4 1
= 2 − r2 e−2r/a0 + re−2r/a0 dr
a0 2 0
Z Z Z a0
4 1 2 −2r/a0 d
= 2 − r e + r e−2r/a0 dr − r e−2r/a0 dr dr
a0 2 dr 0
2
a0
4 1 a0 a
= 2 − r2 e−2r/a0 − r e−2r/a0 − 0 e−2r/a0
a0 2 2 4 0
2
a0 −2 a20 −2 a20 −2 a20

4
= 2 − e − e − e +0+0+
a0 2 2 4 4
= 1 − 5e−2 = 0.3233
Thus, the probability of finding an electron in 1s orbital of a H-atom within

Bohr radius is 0.3233.
4) For the 1s wavefunction, find hri, the average distance of the electron from
the nucleus.
Solution: The average distance of an electron in 1s orbital is
Z∞ 3/2 3/2
1 1 1 1
hri = √ e−r/a0 × r × √ e−r/a0 × 4πr2 dr
π a0 π a0
0
Z∞
4
= 3 r3 e−2r/a0 dr
a0
0
78
Using the standard integration
Z∞
n!
xn e−bx dx = ; (n > −1)
bn+1
0
we can write
Z∞
4
hri = 3 r3 e−2r/a0 dr
a0
0
4 3!
= ×
a30 16a−4
0
3
= a0
2
5) The 2s wavefunction for the H-atom is Ψ2s = N (2 − ar0 )e−r/2a0 , where N is
a constant, r is the distance from the nucleus and a0 is the Bohr radius. Find
the distance from the nucleus, in terms of a0 , at which the radial probability
density shows maxima.
Solution: The radial probability density for the 2s wavefunction of H-atom is
given by 4πr2 Ψ∗2s Ψ2s . The distance at which it is maximum, can be obtained
by taking its derivative with respect to r and setting the result to zero. Thus,
d
4πr2 Ψ∗2s Ψ2s = 0

dr
d 2 r −r/2a0 r −r/2a0
4π r × N (2 − )e × N (2 − )e =0
dr a0 a0
( 2 )
d r
4πN 2 r2 2 − e−r/a0 = 0
dr a0
( )
2 2

d r
2r − e−r/a0 = 0, as 4πN2 6= 0
dr a0
2
r2 2

1 −r/a0 r 2r
2r − − e + e−r/a0 × 2 2r − 2− =0
a0 a0 a0 a0
r2 2r r2

4r −r/a0
2r − − + 2 +4− e =0
a0 a0 a0 a0

r 1
× 2 r2 − 6ra0 + 4a20 e−r/a0 = 0

r 2−
a0 a0
This gives five roots as
(i) r = 0,
(ii) 2 − ar0 = 0 =⇒ r = 2a0
(iii) e−r/a0 = 0 =⇒ r = ∞ √
(iv) and (v) r2 − 6ra0 + 4a20 = 0 =⇒ r = (3 ± 5)a0 = +5.236a0 , −0.764a0
Among these five, (i) r = 0, (ii) r = 20 , (iii) r = ∞ and (v) r = −0.764a0
are not valid. Because, (i) r = 0 indicates nucleus and at nucleus probability
density cannot be maximum.
(ii) r = 2a0 indicates a node, i.e. at this point the wavefunction Ψ2s becomes
zero and hence at this point the probability density cannot be maximum.
(iii) r = ∞ indicates infinite distance from nucleus. At this point too, the
electron density cannot be maximum.
(v) r = −0.764a0 is a negative distance and hence is invalid.
79
Therefore, we are left with only one option i.e. r = 5.236a0 . This is the point
at which the probability density will be maximum.
6) Justify the existence of a non-zero zero point energy in case of a quantum
mechanical oscillator in the light of Heisenberg Uncertainty principle.
Solution: For a one-dimensional quantum mechanical simple harmonic os-
−Bx2 /2
cillator,
√ the ground state wavefunction is given by Ae , where B =
2π mk/h. The expectation value of linear momentum hpx i will be
Z+∞
2 d 2
hpx i = Ae−Bx /2 −i~ Ae−Bx /2 dx
dx
−∞
Z+∞
2
= i~A2 B xe−Bx dx
−∞
The integrand is an odd function and hence the value of the integral will be
zero. Thus, hpx i = 0. Now, we need the expectation value of p2x i.e. hp2x i.
Z+∞ 2

2 −Bx2 /2 2 d −Bx2 /2
hpx i = Ae −~ Ae dx
dx2
−∞
Z+∞
2
= −A2 ~2 e−Bx B 2 x2 − B dx

−∞
Z+∞ Z+∞
2 2
= −A2 B 2 ~2 x2 e−Bx dx + A2 B~2 e−Bx dx
−∞ −∞
√ r
π π
= −A2 B 2 ~2 √ + A2 B~2
B
√ 2B B
2 2 Bπ 2 2
√
= −A ~ + A ~ Bπ
2
1 √
= A2 ~2 Bπ
2
Thus, the uncertainty in linear momentum (∆px ) would be
p
1 2 2√
r
= A ~ Bπ − 0
2
1/4
Bπ
= A~
4
If this uncertainty in linear momentum be taken as the minimum uncertainty
then the minimum energy (Emin ) of the oscillator would be,
∆p2x
Emin =
2m √
A2 ~2 Bπ
=
4m
Since, none of the quantity on the right hand side is zero, the minimum energy
of the quantum mechanical oscillator is not zero. Thus, the oscillator has a
non-zero zero-point energy and is consistent with the Heisenberg uncertainty
principle.
80
2016: 1) For the photoelectric effect in sodium metal the following results were
obtained where Kmax is the maximum kinetic energy of emitted electrons and
1012 Kmax /erg 3.41 1.95

λ/Å 3125 4047
λ is the wavelength of the incident radiation. Calculate Planck’s constant h

and the ‘work function’ for sodium.
Solution: The relation between the maximum kinetic energy (Kmax ) of the
photoelectrons emitted during a photoelectric experiment, wavelength (λ) of
radiation used and the work function (W0 ) is given by
hc
Kmax = − W0 ,
λ
where h and c are Planck’s constant and speed of light in vacuum respectively.
Given, when λ = 3125 × 10−10 m, Kmax = 3.41 × 105 J. and when λ = 4047 ×
10−10 m, Kmax = 1.95 × 105 J. Thus,
5 h × 3 × 1010
3.41 × 10 = − W0
3125 × 10−10
5 h × 3 × 1010
1.95 × 10 = − W0
4047 × 10−10
Note all the quantities are used in MKS unit, hence the value of h and W0
obtained from these two equations will be in J.sec and J respectively. Sub-
tracting the above two equations, we get

5 20 1 1
(3.41 − 1.95) × 10 = h × 3 × 10 −
3125 4047
1.46 × 105 × 4047 × 3125
h=
922 × 3 × 1020
h = 6.675 × 10−12 J.sec
Putting this value of h in one of the above equations we get,
5 6.675 × 10−12 × 3 × 1010

3.41 × 10 = − W0
3125 × 10−10
W0 = 6.408 × 105 + 3.41 × 105 = 9.818 × 105 J
2) Given that M̂ is a linear operator and that M̂ f1 = bf1 and M̂ f2 = bf2

prove that C1 f1 + C2 f2 where C1 and C2 are constants, is an eigenfunction of
M̂ with eigenvalue b.
Solution: Given
M̂ f1 = bf1
M̂ f2 = bf2
M̂ is a linear operator. Thus, we can write
M̂ (C1 f1 + C2 f2 ) = M̂ C1 f1 + M̂ C2 f2
= C1 M̂ f1 + C2 M̂ f2 Since M̂ is a linear operator.
= C1 bf1 + C2 bf2 Using the above eigenvalue equations.
= b (C1 f1 + C2 f2 )
81
Thus, we see that if f1 and f2 be the eigenfunctions of a linear operator M̂
with the same eigenvalue (b), then the linear combination (C1 f1 + C2 f2 ) will
also be an eigenfunction of M̂ with the same eigenvalue (b).
3) Estimate the minimum uncertainty in the x-component of the velocity of
an electron whose position is measured to an uncertainty 1.0 × 10−11 m.
Solution: The required minimum uncertainty in velocity is
~
∆x =
2∆px
h
=
4πme ∆vx
6.626 × 10−34 J.Sec
=
4 × 3.14 × 9.1 × 10−31 kg × 1.0 × 10−11 m
= 5.797 × 106 m
4) A function that becomes infinite at a point must not be quadratically in-
tegrable. Justify or criticize.
Solution:
R ∗ Quadratic integration of a function Ψ means evaluating the value
of Ψ Ψdτ over a certain limit (usually the boundary of the system). The
limit of integration is very important here. If the function has finite values
within the limit of integration then the function will be quadratically inte-
grable but if the function has infinite value at any point within the limit of
integration then the function will not be quadratically integrable within that
limit. And if a function is not quadratically integrable withing the boundary
of the system then the function cannot be used as a valid wavefunction for the
system. If the boundary of the system is from −∞ to +∞ and the function
becomes infinite at a point then it is definite that the function is not quadrat-
ically integrable. However, if the function becomes infinite only at a point
beyond the boundary of the system then the function will be quadratically
integrable and hence can serve as a valid wavefunction for the system.
5) Sketch Ψ and |Ψ2 | for the n = 3 state for a particle in a 1D box (0 ≤ x ≤
L).
Solution: For a particle in a 1D box, the wavefunction of n = 3 state is
given by r
2 3πx
Ψ= sin
L L
2
The required plots of Ψ and |Ψ | are
��
�
� �
6) Identify the locations of nodes in the wavefunction with n = 4 for a particle

in a 1D box.
Solution: The wavefunction for n = 4 state of a particle in a 1D box is given
by r
2 4πx
Ψ(x) = sin
L L
The nodes appear at the points where the wavefunction is zero. The above
function will be zero at points for which 4x/L = an integer or 0. Thus for
82
n = 4 state for a particle in a 1D box, nodes appear at x = 0, L4 , L2 , 3L
4 and L.
The first and last points i.e. x = 0 and x = L are common to any state of
the particle in a 1D box.
7) Which of the functions 6cos4x, 5x3 , 3e−5x , ln2x, sin3x are eigenfunction of
d2
the operator dx 2 ? For each eigenfunction, state the eigenvalue.
Solution: Let us check one by one
d2
6cos4x = −16 × 6cos4x
dx2
d2 3
5x = 30x
dx2
d2 −5x
2
3e = 25 × 3e−5x
dx
d2 1
ln2x = −
dx2 2x2
2
d
sin3x = −9sin3x
dx2
Thus out of the five given funcitons, three of them i.e. 6cos4x, 3e−5x and
d2
sin3x are eigenfunctions of the operator dx 2 with eigenvalues of −16, 25 and
−9 respectively.
8) For a particle in a 2D rectangular box with sides of lengths L and 2L, show
that (2,2) and (1,4) states are ‘accidentlly’ degenerate.
Solution: In a 2D rectangular box, a degeneracy, which occurs due a combi-
nation of symmetry of the box and the quantum numbers is called ‘accidental
degeneracy’. The energy of a particle in a 2D rectangular box in a quantum
state (nx , ny ) is given by
!
2 2 2
h nx ny
E(nx , ny ) = 2
+ 2
8m Lx Ly
Given Lx = L, Ly = 2L. Thus

!
h2 n2x n2y
E(nx , ny ) = +
8m L2 4L2
Thus for the two states (2,2) and (1,4), the energies are
h2 5h2

4 4
E(2, 2) = + =
8m L2 4L2 8mL2
h2 5h2

1 16
E(1, 4) = + =
8m L2 4L2 8mL2
Therefore, the two states (2,2) and (1,4) are accidentally degenerate for a
particle in a 2D rectangular box with lengths L and 2L.
9) Find an expression for hp2x i in the case of n = 2 state of a particle in a 1D
box, without performing an explicit differentiation. Find the numerical value
of hp2x i for a box of length 2.0Å.
Solution: Since for a particle in a 1D box, the energy is solely kinetic, the
expectation value of p2x can be written as
hp2x i = 2mEn ,
83
where m is the mass of the particle and En is the energy of the nth state. For
4h2
n = 2, in a box of length L, we know E2 = 8mL 2 . Therefore, we can write
4h2
hp2x i = 2m
8mL2
h2
= 2
L
For a box of length L = 2.0Å,
(6.626 × 10−34 )2 2
hp2x i = −10 2
J .sec2 /m2
(2.0 × 10 )
= 1.0976 × 10−47 Kg2 m2 sec−2
10) Show that a Bohr orbit for a hydrogen-like atom has a circumference
which is an integral multiple of de Broglie wavelength of the electron moving
around the nucleus.
Solution: The Bohr’s theory demands that an electron exist only in those
orbits around the nucleus, where the angular momentum of the electron is an
integral multiple of h/2π. i.e.
nh
mvr = ,
2π
where m, v, and r are mass of the electron, velocity of the electron and radius
of the orbit respectively. n is the principal quantum number. Now, accord-
ing to de Broglie’s hypothesis, relation between the wavelength of the wave
associated with the moving electron having momentum mv is given by
h
mv =
λ
Combining the two equations, we can write
h h
r=n
λ 2π
2πr = nλ
Thus, the circumference of the Bohr orbit should be an integral multiple of

de Broglie wavelength.
11) The energy of a particle of mass m in a 1D box of length l is measured.
What are the possible values that can result from the measurement if at the
time of measurement, the state function is
1

30 2
i)Ψ = x(l − x) for 0 ≤ x ≤ l
l5
21
2 3πx
ii)Ψ = sin for 0 ≤ x ≤ l
l l
Solution: In case of (i):
84
Zl 21 21
h2 d2

30 30
hEi = x(l − x) − 2 x(l − x)dx
l5 8π m dx2 l5
0
Zl
15h2
= 2 5 x(l − x)dx
2π ml
0
l
15h2 x2 l x3

= 2 5 −
2π ml 2 3 0
5h2
= 2 2
4π ml
In case of (ii):
Z l 12 12
h2 d2

2 3πx 2 3πx
hEi = sin − 2 sin dx
l l 8π m dx2 l l
0
2 Zl
9h 3πx
= 2sin2 dx
8ml3 l
0
Zl
9h2

6πx
= 1 − cos dx
8ml3 l
0
2
9h
=
8ml2
12) Find the expectation value of kinetic energy of the harmonic oscillator in
the ground state. Given
α 1/4 αx2
Ψg = e− 2 ,
π
where α is a constant.
Solution:
Z∞ 1/4
h2 d2 α 1/4 − αx2

α − αx2
2
hT i = e − 2 e 2 dx
π 8π m dx2 π
−∞
Z∞
h2
r
α αx2 αx2
=− 2 e− 2 α2 x2 − α e− 2 dx
8π m π
−∞
Z∞ Z∞
 
h2
r
α 2 2 2
=− 2 α x2 e−αx dx − α e−αx dx
8π m π
 −∞∞ −∞
Z∞

2
r Z
h α 2 2 2
=− 2 2α x2 e−αx dx − 2α e−αx dx
8π m π
2
r √0 r 0
h α 2 π 1 π
=− 2 α 3/2
−α
4π m π 4α 2 α
h2
r r r
α α π α π
=− 2 −
4π m π 4 α 2 α
αh2
=
16π 2 m
85
13) The force constant of a harmonic oscillator of reduced mass 1.5 × 10−27 kg
is 10Nm−1 . Calculate the zero point energy.
Solution: Zero-point energy of a harmonic oscillator is given by
s
1 k
EZP = h ,
2 µ
where h = Planck’s constant, k = force constant and µ = reduced mass.
Putting the given values of k and m and standard value of h in the above
equation, we can write
s
1 −34 10 N.m−1
EZP = × 6.626 × 10 J.Sec ×
2 1.5 × 10−27 kg
= 2.7049 × 10−20 J
14) Find the most probable value of r for 1s electron in a H-atom.
Solution: The wavefunction for an electron in 1s orbital in H-atom is given
by
3/2
1 1
Ψ1s = √ e−r/a0
π a0
Therefore, the most probable value of r will be obtained by differentiating
the radial probability density 4πr2 Ψ∗1s Ψ1s with respect to r and setting it to
zero.
( 3/2 3/2 )
d 1 1 1 1
0= 4πr2 × √ e−r/a0 × √ e−r/a0
dr π a0 π a0
4 d n o
0= 3 r2 e−2r/a0
a0 dr

8 r
0 = 3r 1 − e−2r/a0
a0 a0
It has three roots.
(i) r = 0, this indicates nucleus. The probability of finding electron cannot
be maximum in nucleus. So, this is not a valid root.
(ii) e−2r/a0 =⇒ r = ∞. At infinite distance too, the probability of finding
the electron cannot be maximum. So, this is also not the required point.
(iii) (1 − ar0 ) =⇒ r = a0 . This represents a distance at Bohr radius distance
and is the required most probable value of r.
15) Plot Ψ1s and Ψ2s vs r.
Solution:
��
��
� �
16) Show that Ψ0 and Ψ1 for harmonic oscillator are orthogonal to each other.
Solution: Ψ0 and Ψ1 for harmonic oscillator are given as
α 1/4 2
Ψ0 = e−αx /2
π
α 1/4 √ 2
Ψ1 = 2αxe−αx /2
π
86
In order to show that these two states are orthogonal to each other, the
overlap integral between the two should be zero.
Z∞ 1/4 1/4 √
r
2
Z∞
α 2
α 2 2α 2
e−αx /2 × 2αxe−αx /2 dx = xe−αx dx
π π π
−∞ −∞
The integrand is an odd function of x and hence the value of the definite
integral will be zero. Thus, we see, that the overlap integral between Ψ0
and Ψ1 states of a harmonic oscillator is zero. Hence these two states are
orthogonal to each other.
17) Show that the degree of degeneracy of a H-atom bound state energy level
is n2 (spin consideration being omitted), n =principal quantum number.
Solution: In H-atom, the Hamiltonian commutes with the orbital angular
momentum L̂2 and one of its components (say Lz ). Since, in our case, we
are not considering the spin, the states are designated by values of three
quantum numbers n, l, and ml . For a given value of n, all the states with
l = 0, .., (n − 1) have the same energy. Similarly, for a given value of n, l all
the (2l + 1) states having ml = −l, . . . , +l have the same energies. Therefore,
n−1
(2l + 1) = 1 + 3 + 5 + · · · + (2n − 1) = n2 .
P
degeneracy is
0
2015: 1) Determine, citing reasons, whether the following function is acceptable as

well behaved wavefunction or not within the indicated interval: e−x cosx (0, ∞).
Solution: e−x is a continuous decaying function and cosx is an oscillating
function. Both are single valued, continuous, finite and square integrable
functions within the interval (0, ∞). Therefore, their product e−x cosx is also
single valued, continuous, finite and square integrable within that interval.
Therefore, e−x cosx is an acceptable and well behaved wavefunction.
2) Write down an expression for ‘Compton Shift’ and indicate therein the
parameter ‘Compton Wavelength’. What is the value of scattering angle for
which the Compton shift becomes maximum?
Solution: Compton shift is give by
h
∆λ = (1 − cosθ) ,
me c
where ∆λ = change in wavelength due to Compton effect – also called Comp-
ton shift, h = Planck’s constant, me = mass of the electron, c = speed of
light in vacuum and θ is the scattering angle.
In the above equation, mhe c is called Compton wavelength.
To find the scattering angle for which the Compton shift becomes maximum,
one needs to take derivative of ∆λ with respect to θ and set the result to
zero. Therefore,
d
∆λ = 0
dθ
d h
(1 − cosθ) = 0
dθ me c
h
sinθ = 0
me c
θ = 0◦ or 180◦
When θ = 0◦ , ∆λ = 0 and when θ = 180◦ , ∆λ = 2 mhe c . Thus, the Compton

shift becomes maximum at 180◦ scattering angle.
87
3) Heisenberg uncertainty principle demands that the zero-point energy of a
Harmonic oscillator be non-zero. Explain.
Solution: Please see question 6 of year 2017.
4) Evaluate the commutator: [x̂n , p̂x ].
Solution:
[x̂n , p̂x ] ψ(x) = x̂n p̂x ψ(x) − p̂x x̂n ψ(x)

n d d
= x −i~ ψ(x) + i~ {xx ψ(x)}
dx dx
n dψ(x) n dψ(x) dxn
= −i~x + i~x + i~ψ(x)
dx dx dx
n−1
= i~nx ψ(x)
Thus, [x̂n , p̂x ] = i~nxn−1

5) Photoelectric effect gives a strong evidence in favor of particle nature of
light. Account for the statement.
Solution: Photoelectric effect is the emission of electrons from a metal sur-
face when the surface is illuminated with a light of frequency, greater than
some minimum frequency (characteristics of the metal). It has been observed
that the number of electrons emitted from the metal surface depends only on
the frequency of the incident light and not on the intensity. This observation
is very striking and is in direct contradiction of the wave nature of light. If
light behaves as a wave then the
6) Find the de Broglie wavelength of electrons that have been accelerated
from rest through a potential difference of 1kV.
Solution: The potential different used for accelerating the electron is 1 kV =
1000 V.
Therefore, the kinetic energy of the electron is 1000 eV = 1000 × 1.602 ×
10−19 J. p
The momentum of the electron = 2 × 9.1 × 10−31 kg × 1.602 × 10−16 J =
1.707 × 10−23 kg.m.sec−1 .
−34
h
So, the de Broglie wavelength of the electron will be λ = mv = 6.626×10
1.707×10−23 =
−5
0.6055 × 10 m
7) Show that the wavefunctions corresponding to different eigenvalues of a
Hermitian operator are orthogonal.
Solution: Let ψ and φ be the wavefunctions corresponding to respectively
the different eigenvalues a and b of a hermitian operator Ô.
Ôψ = aψ
Ôφ = bφ
Since Ô is hermitian, we can write

I I ∗
∗
ψ Ôφdτ = φ Ôψ dτ
I I
ψ aφdτ = φ (bψ)∗ dτ
∗
I
(a − b)ψ ∗ φdτ = 0, (a, b are real)
Since a 6= b, I
ψ ∗ φdτ = 0
88
That means the two wavefunctions are orthogonal to each other.
d2
8) If csinax is an eigenfunction of dx 2 , calculate the eigenvalue.
Solution:
d2
2
csinax = −ca2 sinax
dx
Therefore, the eigenvalue is −a2 .
iEt
9) Explain whether the function e ~ Ψ(x) represents a stationary state or not.
Solution: The expectation value of any property hP̂ i of the system in the
iEt
state e ~ Ψ(x) is given by
I n
iEt
o∗ iEt
hP̂ i = e ~ Ψ(x) P̂ e ~ Ψ(x)dτ
I
−iEt iEt
= e ~ Ψ∗ (x)P̂ e ~ Ψ(x)dτ
Note that the operator P̂ is time-independent. Therefore,

I
−iEt iEt
hP̂ i = e ~ e ~ Ψ∗ (x)P̂ Ψ(x)dτ
I
= Ψ∗ (x)P̂ Ψ(x)dτ,
iEt
which is independent of time. Thus, the function e ~ Ψ(x) represents a sta-
tionary state.
14h2
10) Calculate the degeneracy of the level having an energy of 8ma 2 for a par-
ticle of mass m confined in a cubic box of edge length a.

Solution: The energy of a particle of mass m confined in a cubic box of edge
length a, is given by
h2
E(nx , ny , nz ) = n2x + n2y + n2z
8ma2
2
14h
The given energy is 8ma 2 . This energy can be obtained for the following com-
binations of (nx , ny , nz ): (1,2,3),(1,3,2),(2,1,3),(2,3,1),(3,2,1),(3,1,2). That

means the state is 6-fold degenerate.
11) For what molecular phenomenon does the simple harmonic oscillator serve
as model? Mention its limitation in this respect.
Solution: Simple harmonic oscillator serves as a model for molecular vibra-
tions i.e. to model the vibration of bond in a molecule.
This is applicable only for those vibrations which is harmonic that means only
those vibrations which occur at the bottom of the potential energy surface.
In other words, vibrations corresponding to the lower vibrational state. If
there is anharmonicity in the vibration then simple harmonic oscillator can-
not serve as a good model.
12) The radial wavefunction for the 1s orbital of a H-atom is given by
2
R10 (r) = 3/2
e−r/a0
a0
Calculate the average radius of the 1s orbital. Given
Z∞
n!
xn e−ax dx =
an+1
0
89
Solution:
Z∞
hri = R10 (r)rR10 (r)r2 dr
0
Z∞
2 2
= 3/2
e−r/a0 r 3/2
e−r/a0 r2 dr
a0 a0
0
Z∞
4
= 3 r3 e−2r/a0 dr
a0
0
4 3!a40
= ×
a30 16
3
= a0
2
13) Find out hpx i for a harmonic oscillator in its ground state. Given
a 1/4 2
− ax2
Ψg = e .
π
14) Zero point energy of a simple harmonic oscillator does not violate Heisen-
berg uncertainty principle. Justify.
15) Three 2p orbitals of H-atom are
p1 = f1 (r)rcosθ
p2 = f2 (r)rsinθcosφ
p3 = f3 (r)rsinθsinφ
where the terms have their usual significance. Identify them as 2px , 2py and
2pz with reasons.
Solution: The relation between Cartesian and Polar coordinates is
z
!, #, $
x = rsinθcosφ
y = rsinθsinφ
z = rcosθ,
Comparing the angular part of the given three 2p orbitals with the above
relations, one can easily identify that p1 represents py orbital, p2 represents
px orbital and p3 represent pz orbital.
90
16) Define radial distribution function (RDF) and give the plot of RDF cor-
responding to the following wavefunction against r/a0 . Given
Ψ = A(2a0 − r)e−r/2a0
Solution: Radial distribution function is defined as a function that de-

scribes the variation of probability density with distance. For a quantum
mechanical systems in state Ψ(r), the radial distribution function is given by
4πr2 Ψ∗ (r)Ψ(r).
For Ψ(r) = A(2a0 − r)e−r/2a0 , radial distribution function will be
4πA2 (2a0 r − r2 )2 e−r/a0
A plot of this function against r/a0 is

��
��
h i 2
d
2014: 1) Evaluate the commutator Â, B̂ , where Â = dx 2 and B̂ = x.
Solution:
2
h i d
Â, B̂ ψ(x) = , x ψ(x)
dx2
d2 d2
= 2 {xψ(x)} − x 2 ψ(x)
dx dx
d2 ψ(x) d2 ψ(x)
=x + ψ(x) × 0 − x
dx2 dx2
=0
2) The Hamiltonian operator for a system is given by
~2 d2
Ĥ = − .
2m dx2
If it is operated on a wavefunction Ψ = 2l sin nπx
l find dispersion in energy
2 2 2
given by the expression σE = hE i − hEi .
91
Solution:
Zl
~2 d2 2 nπx

2 nπx
hEi = sin − sin dx
l l 2m dx2 l l
0
Zl
2~2 n2 π 2 nπx
= sin2 dx
ml4 l
0
Zl
h2n2

2nπx
= 1 − cos dx
4ml4 l
0
2
l
h2n l 2nπx
= x− sin
4ml4 2nπ l 0
2

h2n l
= l− sin2nπ − 0 + 0
4ml4 2nπ
n2 h2
=
4ml3
and
Zl 2
~2 d2

2 2 nπx 2 nπx
hE i = sin − sin dx
l l 2m dx2 l l
0
Zl
4~4 nπx d4 nπx
= sin sin dx
4m2 l2 l dx4 l
0
Zl
4~4 n4 π 4 nπx
= sin2 dx
4m2 l6 l
0
Zl
h4 n4

2nπx
= 1 − cos dx
32m2 l6 l
0
This is the same integral asappeared above.
h4 n4
=
32m2 l5
So, the dispersion in energy will be
σE = hE 2 i − hEi2
2 2 2
h4 n4 nh
= −
32m2 l5 4ml3
n4 h4 (l − 2)
=
32m2 l6
3) Find whether the following wavefunctions are well-behaved wavefunctions
or not (i) e−x (−∞, ∞), (ii) xe−x (0, ∞).
Solution: (i) e−x becomes infinite at x = −∞. That means, it is not
quadratically integrable in the given interval. So, it is not a well-behaved
wavefunction.
(ii) xe−x is a continuous function. It has also finite values in the indicated
92
interval. it is also quadratically integrable.
Z∞ Z Z Z ∞
−x 2
2 −2x d 2 −2x
xe dx = x e dx − x e dx dx
dx 0
0
∞
1 −2x 2
= − e (2x + 2x + 1)
4 0
1
=
4
So, xe−x is a well-behaved wavefunction.
4) A particle is trapped in a 1D box of length L. Apply de Broglie’s hypothesis
to obtain energy levels.
Solution: For a particle to exist in a 1D box of length L, L should be an
integral multiple of the de Broglie wavelength of the particle. i.e. L = nλ.
h
But λ = mv (de Broglie relation). Let there be a constant potential (V ) inside
mv 2
the box.
p Then the energy of the particle can be written as E = 2 + V =⇒
mv = (E − V )2m Therefore,
nh
L=
mv
2 n2 h2 n2 h2
L = 2 2=
mv 2m(E − V )
n2 h2
E= +V
2mL2
5) Find the expression of permitted energies when (i) an electron is in a box
of 0.01 nm length, (ii) a 10 gm marble is in a box of 10 cm length. Mass of
electron = 9.1 × 10−31 kg.
Solution: The energy of a particle is quantized. According to the particle
in a 1D box model, (i) the expression of permitted energy of an electron in a
box of length 0.01 nm is given by
n2 h2
Eelectron =
8me l2
2
6.626 × 10−34 n2
= J
8 × 9.1 × 10−31 × (0.01 × 10−9 )2
= n2 × 0.603 × 10−15 J
(ii) the expression of permitted energy of a 10 g marble in a box of 10cm
length is given by
n2 h2
Emarble =
8mmarble l2
2
6.626 × 10−34 n2
J
8 × 10 × 10−3 × (10 × 10−2 )2
= n2 × 0.549 × 10−63 J
6) An excited atom gives up excess energy by emitting a photon of character-
istic frequency. The average period that elapses between the excitation of the
atom and the time it radiates is 1.0 × 10−8 sec. Find the inherent uncertainty
in the frequency of the photon.
Solution: According to Heisenberg uncertainty principle, we can write
h
∆E × τ ≥ ,
4π
93
where ∆E is the uncertainty in the energy of the photon emitted and τ is the
average time that elapses between the excitation of the atom and the time it
radiates. Given, τ = 1.0 × 10−8 sec. Using the relation ∆E = h∆ν, where
∆ν is the uncertainty in frequency of the photon. We can write
1
∆ν ≥
4πτ
1
∆ν ≥ −8
sec−1
4 × 3.14 × 1.0 × 10
∆ν ≥ 7.962 × 106 sec−1
7) Show that in a rectangular box with sides L1 = L and L2 = 2L, there is an
accidental degeneracy between the states nx = 1, ny = 4 and nx = 2, ny = 2.
8) Given that the work function of chromium is 4.40 eV, calculate the kinetic
energy of electrons emitted from a chromium surface that is radiated with
UV radiation of wavelength 200 nm.
Solution: Einstein’s equation of photoelectric effect is given by: T = hc
λ −W ,
where T = kinetic energy of the electron emitted, λ = wavelength of light
used, W = work function of the metal, h and c are the Planck’s constant
and speed of light in vacuum respectively. Given, λ = 200 × 10−9 m, W =
4.40eV = 4.40 × 1.602 × 10−19 J. Thus we can write
6.626 × 10−34 J.Sec × 3 × 108 m.sec−1
T = −9
− 4.40 × 1.602 × 10−19 J
200 × 10 m
= 993.9 × 10 − 7.0488 × 10−19 J
−19
= 986.851 × 10−19 J
9) Regard a chain of N conjugated carbon atoms, bond length RCC , as forming
a box of length L = (N − 1)RCC . Find the allowed energies. Estimate the
wavelength of the lowest energy transition.
Solution: The required energy is
n2 h2
En =
8mL2
n2 h2
= 2
8m(N − 1)2 RCC
For estimating the wavelength of the the lowest energy transition, we should
calculate the wavelength for the energy different E2 − E1 . Thus
22 h2 12 h2
E2 − E1 = 2 − 2
8m(N − 1)2 RCC 8m(N − 1)2 RCC
3h2
= 2
8m(N − 1)2 RCC
Thus the required wavelength is
hc 8hcm(N − 1)2 RCC
2
λ= =
E2 − E1 3h2
10) An electron is travelling at 1/4th the speed of light. Calculate the de
Broglie wavelength taking into account the relativistic change in mass.
Solution: For a body moving with velocity v, its mass is given by
m0
M=q ,
v2
1 − c2
94
where m0 is the rest mass of the body i.e. it’s mass when it is at rest v = 0.
Now, if an electron of rest mass me is moving with a velocity v = 41 c, then
the relativistic mass of the electron will become
me
M=q
1
1 − 16
4me
=√
15
Therefore, the required de Broglie wavelength will be
h
λ=
M
√v
15h
=
me c
11) Find and plot the radial distribution function for the following hydrogenic
orbital Ψ = Arcosθe−r/2a0 , where A and a0 are constants.
Solution: The radial part of the given wavefunction is R = Are−r/2a0 . There-
fore, the radial distribution function for the given hydrogenic orbital will be
2
2 2 2 −r/2a0
|R| × 4πr = 4πr Are
= 4πA2 r4 e−r/a0
The required plot is
��
12) Normalize the wavefunction of a harmonic oscillator in the v = 1 level,

2
ψ1 = Axe−ax /2 . Given,
Z∞ r
2 −ax2 1 π
xe dx =
4a a
0
Solution:
Z+∞ 2
−ax2 /2
Axe dx = 1
−∞
Z+∞
2
A2 x2 e−ax dx = 1
−∞
Z+∞
2
A2 × 2 x2 e−ax dx = 1
0
r
21 π
2A =1
4a a
3 1/4
4a
A=
π
95
13) The wavefunction for 2pz orbital of H-atom is
1
ψ2pz = p re−r/2a0 cosθ,
32πa50
where a0 =Bohr radius. Find the average value of the electron-nucleus sepa-
R∞ n −bx n!
ration in the 2pz orbital of H-atom. Given x e dx = bn+1 .
0
Solution:
Z∞ Zπ Z2π
1 −r/2a0 1
hri = p
5
re cosθ × r × p
5
re−r/2a0 cosθ × r2 sinθdrdθdφ
32πa0 32πa0
0 0 0
Z∞ Zπ Z2π
1
= r5 e−r/2a0 dr sinθcos2 θdθ dφ
32πa50
0 0 0
3
π
1 6 6 cos θ
= × 5! × 2 a 0 × − × 2π
32πa50 3 0
= 320a0
14) For a harmonic oscillator consisting of a particle of mass 1.33 × 10−25 kg.,
the difference in adjacent energy levels is 4.82 × 10−21 J. Calculate the force
constant of the oscillator.
Solution: The energy difference between two adjacent states of a harmonic
oscillator consisting of mass m and oscillating with frequency ω, in v th state
is given by
r
k
∆Ev,v+1 = hω, where ω = Thus,
m
2
m∆Ev,v+1
k=
h2
Given, m = 1.33 × 10−25 kg and ∆Ev,v+1 = 4.82 × 10−21 J. Therefore,
1.33 × 10−25 × (4.82 × 10−21 )2
k=
(6.626 × 10−34 )2
= 7.037 kg.sec−2
15) The wavefunction for the state of lowest energy of 1D harmonic√ oscillator
2
is ψ = Ae−Bx , where A is the normalization constant and B q = 2hkµ . Show
that the total energy E of the lowest state is 21 hω, where ω = µk .
16) ‘p-orbitals are not designated as p0 , p+1 , p−1 but as px , py , pz .’ Explain.
Solution: The px , py and pz representation is based on the orientation of
the lobes of the three p orbitals along the three Cartesian axes, whereas the
p0 , p+1 and p−1 representation is based on the value of magnetic quantum
number. It has been found that the wavefunction corresponding to p0 is a
real function but those corresponding to p+1 and p−1 are imaginary functions.
In order to convert the imaginary functions into real functions, linear com-
binations of p+1 and p−1 are taken, which results in two functions, whose
spherical harmonics, when plotted, gives lobes along x and y axes. These
two linear combinations are therefore named as px and py respectively. The
spherical harmonics of p0 function has lobes along the z axis and hence is
called pz orbital.
96
2013: 1) Determine whether each of the following functions is acceptable or not as a
state function over the indicated intervals: (i) e−|x| (−∞, ∞), (ii) cos−1 x[−1, 1]
Solution: (i) The function e−|x| is not differentiable at x = 0 and hence is
not an acceptable as a state function.
(ii) The function cos−1 x in the interval of [−1, 1] is continuous and finite. It
is also quadratically integrable.
Z+1
cos−1 x × cos−1 xdx
−1
1
Let z = cos−1 x =⇒ dz = − √1−x 2
dx =⇒ dx = −sinzdz. Therefore,
Z+1 x=+1
Z
cos−1 x × cos−1 xdx = − z 2 sinzdz
−1 x=−1
Z Z Z x=+1
d
= − z 2 sinzdz − z 2 sinzdz dz
dz x=−1
Z x=+1
= − −z 2 cosz + 2 zcoszdz
x=−1
Z Z Z x=+1
d
= − −z 2 cosz + 2z coszdz − 2 z coszdz dz
dz x=−1
x=+1
= − −z 2 cosz + 2zsinz + 2cosz x=−1

h 2 p ix=+1
−1 2 −1
= x cos x − 2 1 − x cos x − 2x
x=−1
2 2
= 0 − 0 − 2 − π + 0 − 2 = −(π + 4)
Hence cos−1 x, [−1, 1] is an acceptable state function.

2) Prove that the functions Ψn (x) = (2a)−1/2 eiπnx/a , n = 0, ±1, ±2, ... over
the interval −a ≤ x ≤ a are each normalized and mutually orthogonal. problem
Solution: (i) Normalization:
Z+a Z+a
1 2iπnx
|Ψn (x)|2 dx = e a dx
2a
−a −a
1 a h 2iπnx i+a
= × e a
2a 2iπn −a
1
e2iπn − e−2iπn

=
4inπ
1
= sin2nπ = 0
2nπ
97
(ii) For orthogonality:
Z+a Z+a
1 iπmx iπmx
Ψm (x)Ψn (x)dx = e a e a dx
2a
−a −a
Z+a
1 iπ(m+n)x
= e a dx
2a
−a
1 a h iπ(m+n)x i+a
= × e a
2a iπ(m + n) −a
a
iπ(m+n) −iπ(m+n)

= e −e
iπ(m + n)
2a
= sin{(m + n)π}
π(m + n)
= 0 as both m and n are integers.
Thus the functions are orthogonal to each other but are not normalized.
3) Benzene may be regarded as a square box of 4Å edge length containing
6π electrons. Find the expression for the energy of the ground state of the
system. Calculate the minimum energy required to promote one electron to
the lowest unoccupied energy level.
Solution: The energy of a particle in a 2D square box of length L is given
by
n2x + n2y h2

E(nx , ny ) =
8mL2
Since there are six electrons, the first three energy levels will be occupied
by them. Therefore, the lowest unoccupied energy level is the fourth energy
level. The quantum numbers corresponding to first four energy levels are
(nx = 1, ny = 1), (nx = 1, ny = 2), (nx = 2, ny = 1), and (nx = 2, ny = 2).
Thus, the minimum energy required to promote one electron to the lowest
unoccupied energy level corresponds to the energy different between the levels
(nx = 1, ny = 2) and (nx = 2, ny = 2). Therefore,
22 + 22 h2 12 + 22 h2

E(2, 2) − E(1, 2) = −
8mL2 8mL2
3h2
= .
8mL2
Given L = 4Å= 4.0 × 10−10 m, m = 9.1 × 10−31 kg.
3(6.626 × 10−34 )2
E(2, 2) − E(1, 2) = J
8 × 9.1 × 10−31 × (4.0 × 10−10 )2
= 11.31 × 10−19 J
4) Prove that a Hermitian operator produces eigenvalues that are real.

Solution: Let Â be a hermitian operator and ψ be a normalized eigenfunction
of Â with eigenvalue a. Then we’ll have to prove that a is real. From the
98
definition of hermitian operator, we can write,
I I ∗
∗
ψ Âψdτ = ψ Âψ dτ
I I
ψ aψdτ = ψ(aψ)∗ dτ
∗
I I
∗ ∗
a ψ ψdτ = a ψψ ∗ dτ
I
(a − a ) ψ ∗ ψdτ = 0
∗
Since ψ is normalized, ψ ∗ ψdτ 6= 0. This means a − a∗ = 0 =⇒ a = a∗ ,

H
which is possible only when a is real.
5) Explain what you understand by Compton effect. Determine the scattering
angle for which the shift in wavelength would be maximum.
Solution: Compton effect is the change in wavelength of an x-ray when it is
scattered by an electron. The amount by which wavelength changes is called
Compton shift.
For second part, please see question 2 of year 2015.
6) Evaluate hpx i for a particle confined in a 1D box.
Solution: For a particle in a 1D box of length
q L (along x-axis, between x = 0
2 nπx
to x = L), the wavefunction is given by L sin L
ZL r r
2 nπx h d 2 nπx
hpx i = sin −i sin dx
L L 2π dx L L
0
ZL
ih nπ nπx nπx
=− × sin cos dx
πL L L L
0
ZL
inh 2nπx
=− 2 sin dx
2L L
0
ih
= (cos2nπ − cos0)
4πL
=0
7) Draw the Ψ and Ψ2 plots as a function of x for the particle in a 1D box,

(0 ≤ x ≤ L) in the state n = 2. Determine the slopes of Ψ and Ψ2 at
x = 0, L/2.
Solution: Slope of ψ and ψ 2 at x = 0, L/2
��
�
� �
99
r √
d 2 2π 2πx 2π 2
ψ = × cos = √
dx L L L

x=0 x=0
L L
r √
d 2 2π 2πx 2π 2
ψ = × cos =− √
dx L L L

x=L/2 x=L/2
L L

d 2 2 2πx 2πx 2π
ψ = × 2 × sin × cos × =0
dx x=0 L L L L x=0

d 2 2 2πx 2πx 2π
ψ = × 2 × sin × cos × =0
dx x=L/2 L L L L x=L/2
8) The kinetic energy of an electron trapped in a cubical box of edge-length

‘a’ is given as E = 14h2 /8ma2 . How many degenerate states do you expect?
9) Consider a particle with quantum number ‘n’ moving in a 1D box of
length ’l’. (i) Determine the probability of finding the particle in the region,
0 ≤ x ≤ l/4. (ii) For what value of ‘n’, the above determined probability is a
maximum.
Solution:(i) Probability of finding the particle in the region, 0 ≤ x ≤ l/4 is
given by
Zl/4r r
2 nπx 2 nπx
P (0 ≤ x ≤ l/4) = sin × sin dx
l l l l
0
Zl/4
1 2nπx
= 1 − cos dx
l l
0
l/4
1 l 2nπx
= x− sin
l 2nπ l 0

1 l l nπ
= − sin −0+0
l 4 2nπ 2
1 1 nπ
= − sin
4 2nπ 2
(ii) The value of sine function lies between 0 and 1. So, the above probability
will be maximum when sin nπ 2 = 0, which is possible for all the even values of
n i.e. n = 2, 4, 6, ...
1/4 −αx2 /2
10) Justify that the harmonic oscillator wavefunctions ψ0 (x) = απ e
3 1/4 2
and ψ1 (x) = 4απ xe−αx /2 are orthogonal.
11) The radial wavefunction for the 1s orbital of a hydrogen atom is given by
2
R10 (r) = 3/2
e−r/a0
a0
Calculate the probability that an electron described by a hydrogen atomic 1s
wavefunction will be found within one Bohr radius (a0 ) of the nucleus.
100
Solution:
Za0 Za0
4
|R10 (r)|2 r2 dr = 3 r2 e−2r/a0 dr
a0
0
Z0 Z Z a0
4 2 d
= 3 r e−2r/a0 dr − r2 e−2r/a0 dr dr
a0 dr
Z a0 0
4 a0 a0
= 3 r2 − e−2r/a0 − 2r − e−2r/a0 dr
a0 2 2 0
Z a0
4 1
= 2 − r2 e−2r/a0 + re−2r/a0 dr
a0 2 0
Z Z Z a0
4 1 2 −2r/a0 −2r/a0 d −2r/a0
= 2 − r e +r e dr − r e dr dr
a0 2 dr 0
2
a0
4 1 a0 a
= 2 − r2 e−2r/a0 − r e−2r/a0 − 0 e−2r/a0
a0 2 2 4 0
2 2 2 2

4 a0 −2 a0 −2 a0 −2 a0
= 2 − e − e − e +0+0+
a0 2 2 4 4
= 1 − 5e−2 = 0.3233
12) What is the zero-point energy of a particle executing simple harmonic

oscillations?
Solution: Zero-point energy of a particle executing simple harmonic oscilla-
tions is 21 hω, where h = Planck’s constant and ω = frequency at which the
oscillator oscillates.
13) Calculate the most probable radius (rmp ), at which an electron will be
found when it occupies a 1s orbital of a hydrogenic atom of atomic number
Z. 3/2
1 Z
ψ1s = √ e−zr/a0
π a0
Solution: The wavefunction for an electron in 1s orbital in a hydrogenic
atom is given by
3/2
1 Z
Ψ1s = √ e−r/a0
π a0
Therefore, the most probable value of r will be obtained by differentiating
the radial probability density 4πr2 Ψ∗1s Ψ1s with respect to r and setting it to
zero.
( 3/2 3/2 )
d 1 Z 1 Z
0= 4πr2 × √ e−r/a0 × √ e−r/a0
dr π a0 π a0
4Z 3 d n 2 −2r/a0 o
0= 3 r e
a0 dr
8Z 3

r
0= 3 r 1− e−2r/a0
a0 a0
It has three roots.

(i) r = 0, this indicates nucleus. The probability of finding electron cannot
be maximum in nucleus. So, this is not a valid root.
(ii) e−2r/a0 =⇒ r = ∞. At infinite distance too, the probability of finding
the electron cannot be maximum. So, this is also not the required point.
(iii) (1 − ar0 ) =⇒ r = a0 . This represents a distance equal to Bohr radius
101
and is the required most probable value of r.
14) Calculate the frequency of radiation emitted when a harmonic oscillator
of frequency 6.0 × 1013 Sec−1 goes from v = 8 to v = 7 level.
Solution: The energy gap between two adjacent states of a harmonic oscil-
lator is given by ∆E = hω, where h = Planck’s constant and ω = frequency
of oscillation. If ν be the frequency of the light emitted due to this change of
state, then ∆E = hν. Therefore, the frequency of light emitted will be the
same as the frequency of oscillation of the oscillator i.e 6.0 × 1013 Sec−1 .
15) The radial part of the 2s and 2p orbitals of hydrogen atom are given (in
a.u.) as: R20 = N1 (2 − r)e−r/2 and R21 = N2 re−r/2 , where N1 and N2 are
constants. Depict graphically the plots of the radial distribution functions
against r and comment.
Solution: The required plot is
��
��
��
(i) The figure clearly shows that 2s orbital has one node at r = 2, whereas 2p
orbital has no node and 2s also has larger electron density near the nucleus
than 2p orbital.
(ii) The electron density in 2p orbital also spans into the region of 2s orbital,
which reflects that 2s electron does not screen the 2p orbitals completely.
(iii) At large distance, the probability density decreases must faster for the
2p orbital than 2s orbital.
2012: 1) Consider a particle of mass m confined in an infinitely deep potential
well, where V = 0 for |x| < L: The wavefunction is of the form Ψ(x) =
Asinkx + Bcoskx. Apply boundary condition on the wavefunction to deduce
that k = nπ
2L , n = 0, 1, 2, . . . with A = 0 for odd n, and B = 0 for even n.
Solution: The given wavefunction is
Ψ(x) = Asinkx + Bcoskx
The boundary conditions are (i) when x = L, Ψ(x) = 0 and (ii) when x =
−L, Ψ(x) = 0. Application of these conditions on Ψ(x) gives:
0 = AsinkL + BcoskL Condition (i)

0 = −AsinkL + BcoskL Condition (ii)
From these two equations, we get
AsinkL = 0, On subtracting the above two equations

BcoskL = 0, On Adding the above two equations
It is obvious that both A and B cannot be zero – as it will make the whole
wavefunction zero. So, The above two equations says that –
(i) If A = 0, B 6= 0 and hence coskL = 0 =⇒ kL = nπ2 , when n is odd.
(ii) If B = 0, A 6== 0 and hence sinkL = 0 =⇒ kL = nπ, when n is any
102
integer. The second part can be modified as kL = nπ 2 , when n is even.
2) Determine, citing reasons, whether each of the following functions is ac-
ceptable or not as a wavefunction over the indicated intervals: sin−1 x, [−1, 1]
and 1/x[0.∞].
Solution: (i) The function sin−1 x in the interval of [−1, 1] is continuous and
finite. It is also quadratically integrable.
Z+1
sin−1 x × sin−1 xdx
−1
Let z = sin−1 x =⇒ dz = √ 1 dx
1−x2
=⇒ dx = coszdz. Therefore,
Z+1 x=+1
Z
sin−1 x × sin−1 xdx = z 2 coszdz
−1 x=−1
Z Z Z x=+1
d
= z 2 coszdz − z 2 coszdz dz
dz x=−1
Z x=+1
= z 2 sinz − 2 zsinzdz
x=−1
Z Z Z x=+1
d
= z 2 sinz − 2z sinzdz + 2 z sinzzdz dz
dz x=−1
2 x=+1
= z sinz + 2zcosz − 2sinz x=−1
h 2 p ix=+1
−1 2 −1
= x sin x + 2 1 − x sin x − 2x
x=−1
2 2 2
π π π
= +0−2+ −0−2= −4
4 4 2
Hence sin−1 x, [−1, 1] is an acceptable state function.
(ii) 1/x, [0, ∞] becomes ∞ at x = 0. So, it is not an acceptable wavefunction.
3) The de Broglie wavelength of the electron moving in the first orbit of the
hydrogen atom (Bohr model) is equal to the circumference of the orbit. Jus-
tify.
4) The term ‘state’ and ‘energy level’ are not synonymous in quantum me-
9h2
chanics. For the particle in a cubic box, consider E ≤ 8ma 2 . How many states
and levels lie within this range?

Solution: For a particle of mass m in a cubic box of length, the expression
for energy is given by
h2
E= n2x + n2y + n2z + ,
8mL2
where nx , ny and nz are the three principal quantum numbers along the three
9h2
Cartesian coordinate axes. For E ≤ 8ma 2 , the following combinations of nx , ny
and nz are possible – (1,1,1),(1,2,2),(2,1,2),(2,2,1). So, there are four energy

levels and two states. The two states are non-degenerate ground state (1,2,2)
and three-fold degenerate first excited state {(1,2,2),(2,1,2),(2,2,1)}.
5) Light of wavelength 552 nm or greater will not eject photoelectrons from
a potassium surface. What is the work function (in eV) of potassium?
103
Solution: The required work function (W0 ) is
6.626 × 10−34 J.Sec × 3.0 × 108 m.Sec−1

W0 =
552 × 10−9 m
= 3.601 × 10−19 J
6) Evaluate the expectation value of momentum of a particle described by

2
the wavefunction e−ax , where x ranges from −∞ to ∞.
Solution:
Z+∞
2 h d 2
hpx i = e−ax −i e−ax dx
2π dx
−∞
Z+∞
ih −ax2

−ax2

=− e × −2axe dx
2π
−∞
+∞
Z
iah 2
= xe−2ax dx
π
−∞
= 0 The integrand is an odd function of the variable.
d
7) Define a hermitian operator. Confirm that the operator, ~i dx is hermitian.
Solution: (i) Hermitian operator: A hermitian operator is one which obeys
the turn-over rule. That means, if f and g be two functions and Â be a
hermitian operator then
I I ∗
∗
f Âgdτ = g Âf dτ.
In other words, an operator is said to be hermitian if it is self-adjoint i.e.

Â∗ = Â, where ∗ represents taking complex conjugate.
(ii) Let f (x) and g(x) be the two functions. Then, For the given operator
d
Â = ~i dx , we can write,
Z+∞ Z+∞
~ d ~
f ∗ (x) g(x)dx = f ∗ (x)dg(x)
i dx i
−∞ −∞
Z Z ∗ Z +∞
~ ∗ df (x)
= f (x) dg(x) − dg(x) dx
i dx −∞
Z ∗
+∞
~ ∗ df (x)
= f (x)g(x) − g(x)dx
i dx −∞
Z +∞
~ ∗
= f (x)g(x) − g(x)df ∗ (x)
i −∞
The first term will vanish at the two limits because the wavefunction for a
confined particle vanishes at very large distance. Thus
Z+∞ Z+∞
~ d ~
f ∗ (x) g(x)dx = − g(x)df ∗ (x)
i dx i
−∞ −∞
104
On analogy to the first step we take, we can write
Z+∞ Z+∞ Z+∞
~ d ~ ~ d ∗
f ∗ (x) g(x)dx = − g(x)df ∗ (x) = − g(x) f (x)
i dx i i dx
−∞ −∞ −∞
Z+∞ ∗
~ d
= g(x) f (x) dx
i dx
−∞
Thus,
Z+∞ Z+∞ ∗
~ d ~ d
f ∗ (x) g(x)dx = g(x) f (x) dx
i dx i dx
−∞ −∞
d
Hence, ~i dx is hermitian.
8) Two operators A and B have simultaneous eigenfunction with different
eigenvalues. Show that A and B commute.
Solution: Let, ψ be an eigenfunction of the two operators Â and B̂ with
eigenvalues a and b respectively and a 6= b. Thus we can write
Âψ = aψ
B̂ψ = bψ
Therefore, we can write
h i
Â, B̂ ψ = ÂB̂ − B̂ Â ψ
= ÂB̂ψ − B̂ Âψ
= Âbψ − B̂aψ
= bÂψ − aB̂ψ
= baψ − abψ
=0
Thus, if two operators A and B have simultaneous eigenfunction with different
eigenvalues then they will commute with each other.
9) For a particle of mass m in a cubic box of length L with zero potential
inside and infinite potential on the walls and outside,show that if the cube is
distorted in Z direction only by an amount ∆L and if ∆L is small, then the
energy changes approximately by
n2z h2
∆E = − ∆L
4mL3
State explicitly the assumption you make in deriving this result.
Solution: The energy of a particle of mass m in a cubic box of length L with
zero potential inside and infinite potential on the walls and outside is given
by
2 2 2
h2
E (nx , ny , nz ) = nx + ny + nz
8mL2
If the box is distorted in Z direction by an amount of ∆L, then the energy of
the elongated box can be written as
h2 n2z h2
E∆L (nx , ny , nz ) = n2x + n2y +
8mL2 8m(L + ∆L)2
105
Here, it is assumed that the change in length is very small, so that we can
still consider that the box to be cubic. Therefore, change in energy will be
∆E = E (nx , ny , nz ) − E∆L (nx , ny , nz )
h2 h2 n2z h2
= n2x + n2y + n2z − n2
x + n 2
y +
8mL2 8mL2 8m(L + ∆L)2
n2z h2 n2z h2
= −
8mL2 8m(L + ∆L)2
n2z h2 1

1
= −
8m L2 (L + ∆L)2
n2z h2 (L + ∆L)2 − L2
= ×
8m L2 (L + ∆L)2
n2 h2 2L∆L + ∆L2
= z × 2
8m L (L + ∆L)2
Since, the change in length is very small, we can neglect ∆L2 and L+∆L ∼ L.
Thus
n2z h2 2L∆L
∆E = ×
8m L4
2 2
nh
= z 3 ∆L
4mL
2 2 2
10) For a particle in a 1D box of length L, hpi = 0 and hp2 i = n Lπ 2~ . Find the
uncertainty in momentum and estimate the zero point energy of the particle.
Solution: The required uncertainty is given by
p
∆p = hp2 i − hpi2
r
n2 π 2 ~2
= −0
L2
nπ~
=
L
nh
=
2L
If this is the minimum uncertainty in momentum, then the minimum energy
i.e. zero-point energy (ZPE) of the particle will be
∆p2
EZPE =
2m
n2 h2
=
8mL2
2011: 1) What is Compton effect? Use a properly labelled diagram to illustrate

your answer. Define Compton wavelength and determine its value.
Solution: Compton effect is the change in wavelength of an x-ray when it is
scattered by an electron. The amount by which wavelength changes is called
Compton shift. The Compton shift is given by
h
∆λ = λf − λi = (1 − cosθ) ,
me c
h
The value of Compton shift for a scattering angle of 90◦ i.e the quantity me c
is called Compton wavelength. Putting the value of h, me and c, we get
106
n
oto
ph
d
re
tt e
a
Sc
𝜆$
Incident photon
𝜃
Electron
at rest Recoil
𝜆# electron
−34
Compton wavelength = 9.1×106.626×10 J.Sec
−31 kg×3.0×108 m.Sec−1 = 0.2427 × 10
−11
m
d
2) Examine which of the following operators are linear: dx , SQR (i.e. squar-
ing)
Solution: If f and g are two functions and c1 and c2 are two constants then
d df dg d
(i) dx {c1 f + c2 g} = c1 dx + c2 dx . Thus, dx is a linear operator.
2
(ii) (c1 f + c2 g) = c1 f + c2 g + 2c1 c2 f g 6= c21 f 2 + c22 g 2 . Thus, SQR is not a
2 2 2 2
linear operator. d d

3) Evaluate the commutator dx + x, dx −x .
Solution:

d d d d d d
+ x, −x ψ = +x −x ψ− −x +x ψ
dx dx dx dx dx dx

d dψ d dψ
= +x − xψ − −x + xψ
dx dx dx dx
d dψ dψ d d dψ dψ d
= +x − (xψ) − x2 ψ − +x − (xψ) +
dx dx dx dx dx dx dx dx
dψ d
= 2x − 2 (xψ)
dx dx
dψ dψ
= 2x − 2x − 2ψ
dx dx
= 2ψ

d d
=⇒ + x, −x =2
dx dx
4) Determine whether the following functions are acceptable over the indi-
cated intervals: ex (−∞, 0), tanθ(0, π/2).
Solution: (i) ex is a continuous and finite function in the given interval
107
(∞, 0). It is also quadratically integrable, as shown below.
Z0 Z0
ex × ex dx = e2x dx
−∞ −∞
1 2x 0
= e −∞
2
1 0
e − e−∞

=
2
1
= (1 − 0)
2
1
=
2
Thus, ex , (−∞, 0) is an acceptable function over the indicated interval.
(ii) The function tanθ in the interval (0, π/2) becomes infinite at θ = π2 . So,
tanθ in the interval (0, π/2) is not an acceptable function.
5) The speed of a certain proton is 4.5 × 105 m/sec. If the uncertainty in its
momentum is to be reduced to 0.01 percent, what uncertainty in its location
must be tolerated? Given, mass of a proton = 1.673 × 10−27 kg
Solution: Let the initial uncertainty in position and momentum of the proton
be ∆x and ∆px respectively. According to Heisenberg uncertainty principle,
h
we can write: ∆px ∆x ≥ 4π .
If we reduce the uncertainty in momentum then corresponding uncertainty in
position can be increased such that Heisenberg uncertainty principle holds.
Let us consider that if the uncertainty in momentum be reduced by 0.01%
then the corresponding increase in uncertainty be w%. Therefore, new un-
certainty in momentum = ∆px − 0.01∆p 100
x
= 0.9999∆px and new uncertainty
(w+100)∆x
in position = ∆x + w∆x
100 = 100 . Again, applying Heisenberg uncertainty
principle, we can write
(w + 100)∆x h
0.9999∆px × ≥
100 4π
0.9999(w + 100) h h
≥
100 4π 4π
0.9999(w + 100)
≥1
100
100
w≥ − 100
0.9999
w ≥ 0.01
Thus, if the uncertainty in momentum be reduced by 0.01% then the corre-

sponding uncertainty in position can be increased to 0.01%.
6) A certain system is described by a Hamiltonian operator
d2
Ĥ = 2 + x2
dx
2
(i) Show that Ψ = Axe−x /2 is an eigenfunction of Ĥ; determine the eigen-
value.
(ii) Determine A, so that the function is normalized.
Z∞ r
2 1 π
x2 e−ax dx =
4 a3
0
108
Solution: (i)
d2

2 −x2 /2
ĤΨ = + x Axe
dx2
d 2 −x2 /2 −x2 /2
2
=A −x e +e + Ax3 e−x /2
dx
2 2 2
= A 1 − x2 e−x /2 (−x) + Ae−x /2 (0 − 2x) + Ax3 e−x /2

2 2 2 2
= −Axe−x /2
+ Ax3 e−x /2
− 2Axe−x /2
+ Ax3 e−x /2
2 2
= 2Ax3 e−x /2 − 3Axe−x /2
= (2x2 − 3)Ψ
Thus Ψ is an eigenfunction of Ĥ and the eigenvalue is (2x2 − 3).

(ii)
Z∞
Ψ2 dx = 1
0
Z∞ 2
−x2 /2
Axe dx = 1
0
Z∞
2
A2 x2 e−x dx = 1
0
1√
A2 π=1
4
2
A=±
π 1/4
7) Draw the Ψ and Ψ2 plots as a function of x for the article in a 1D box

(0 ≤ x ≤ L): in the state n = 2. Determine the slopes of Ψ and Ψ2 at
x = 0, L/2. Prove that the maximum and minimum for Ψ occur at L/4 and
3L/4 respectively.
Solution: Part (i) and (ii): Please see question 7 of year 2013. q
2 2πx
Part (iii): Ψ for n = 2 state for a particle in a 1D box of length L is, L sin L .
At extreme points of Ψ,
r
d 2 2πx
sin =0
r dx L L
2 2π 2πx
× cos =0
L L L
2πx
cos =0
L
2πx (2m + 1)π
= , m = 0, 1, 2, ...
L 2
L
x = (2m + 1)
4
Since x > L is not allowed, only two values of m i.e. 0 and 1 are valid.
Since, the second derivative of Ψ will always be negative (derivative of cosine
function is negative of sine function), maxima will occur at L/4 and at 3L/4.
8) An electron in a 3D rectangular box with dimensions 5Å, 3Å and 6Å
makes a radiative transition from the lowest excited state to the ground state.
109
Calculate the frequency of the photon emitted.
Solution: Ground state of a particle i a 3D box corresponds to (1,1,1) state
and the lowest excited state corresponds to (1,1,2) state. Further, the energy
of the particle in (nx , ny , nz ) state is given by
!
2 2
nx ny nz h2
2
E(nx , ny , nz ) = + +
L2x L2y L2z 8m
Given Lx = 5Å, Ly = 3Å, Lz = 6Å0.0455. Therefore, the required frequency

of the photon emitted is given by
E(1, 1, 2) − E(1, 1, 1)
ν=
h
h 1 1 4 1 1 1
= + + − + +
8m L2x L2y L2z L2x L2y L2z
3h 3 × 6.626 × 10−34 J.Sec
= =
8mL2z 8 × 9.1 × 10−31 kg × (6 × 10−10 m)2
= 7.58 × 1014 Sec−1
9) Find the most likely location of a particle in a 1D box of length ‘L’ in the
ground state.
Solution: The most likely position of a particle in a 1D box can be obtained
by setting the first derivative of probability density i.e. |Ψ(x)|2 to zero. Thus,
for ground state

d 2 2 πx
sin =0
dx L L
2 πx πx π
× 2sin × cos × =0
L L L L
2πx
sin =0
L
2πx
=⇒ = mπ, where m = 0, ±1, ±2, ±3, ...
L
mL
x=
2
m = 0 gives x = 0 i.e one of the wall of the box and since, at the wall,
potential is infinite, the particle cannot exist there. Furthermore, since x
cannot be larger than or equal to the length of the box, only m = +1 is the
allowed value for m. Thus, the most likely location of a particle in a 1D box
is x = L/2 i.e at the center of the box.
10) For a H-atom identify the following orbitals with given radial parts as
(i) N2 β2 re−α2 r and (ii) N3 re−α3 r , where Ni , βi , αi are constants. Explain your
answer using the plots of the orbitals. weird
Solution:
2010: 1) Examine whether the following are acceptable wavefuncitons: (i) sin−1 x [−1 ≤ x ≤ 1
(ii) 1/x[0 < x < ∞].
Solution: Please see question 2 of year 2012
2) The de Broglie wavelength of the electron moving in the first orbit of the
hydrogen atom (Bohr orbit) is equal to the circumference of the orbit. Jus-
tify.
3) Zero point energy of a harmonic oscillator is a consequence of uncertainty
110
principle. Explain.
4) Verify whether the squaring operator, ( )2 is linear or not.
5) Find the value of the commutator [x̂, p̂x ].
Solution:
[x̂, p̂x ] ψ(x) = x̂p̂x ψ − p̂x x̂
dψ d
= −i~x + i~ (xψ)
dx dx
dψ dψ
= −i~x + i~x + i~ψ
dx dx
= i~ψ
=⇒ [x̂, p̂x ] = i~
6) Find the radial distribution function for the following hydrogenic orbital,
Ψ = Arcosθe−r/2a0 , where A and a0 are constants.
7) “If φ1 and φ2 are degenerate eigenfunctions of a linear operator Â, then
a linear combination of the eigenfunctions is also an eigenfunction of the
operator with the same eigenvalue.” Prove the statement.
8) For a particle in a 1D box, show that Ψm and Ψm−1 are orthogonal to each
other.
Solution:
ZL ZL r r
2 mπx 2 (m − 1)πx
Ψm Ψm−1 dx = sin sin dx
L L L L
0 0
ZL
1 mπx (m − 1)πx
= 2sin sin dx
L L L
0
ZL
(2m − 1)πx

1 πx
= cos − cos dx
L L L
0

1 L L L L
= sinπ − sin0 − sin(2m − 1)π + sin0
L π π (2m − 1)π (2m + 1)
=0
Thus, the two wavefunctions in questions are orthogonal to each other.

9) For a particle of mass ‘m’, confined in a 1D box of length ‘L’ find the
value of ∆px , where ∆p2x = hp2x i − hpx i2 and hpx i is zero. Hence determine
the minimum possible value of ∆x for the third level.
111
Solution: For a particle in a 1D box
ZL r r
2 nπx 2 nπx
hp2x i = sin p̂2x sin dx
L L L L
0
ZL 2
2 nπx d nπx
= sin −i~ sin dx
L L dx L
0
ZL
2~2
2 2
nπx nπ nπx
=− sin × − 2 × sin dx
L L L L
0
ZL
n2 ~2 π 2 nπx
= 2sin2 dx
L3 L
0
ZL
n2 ~2 π 2

2nπx
= 1 − cos dx
L3 L
0
2 2 2
L
n2 ~2 π 2 n2 h2

n~π L 2nπx
= x− sin = =
L3 2nπ L 0 L2 4L2
Therefore,
p
hp2 i − hpx i2
∆px =
r x
n2 h2
= −0
4L2
nh
=
2L
According to Heisenberg uncertainty principle, we can write
h
∆px ∆x ≥
4π
nh h
∆x ≥
2L 4π
L
∆xmin =
2nπ
L
Thus, for n = 3, ∆xmin = 6π .
10) What is the frequency of the light absorbed when a CO molecule (assumed
to be a rigid rotor) makes a transition from the rotational ground state to
the first excited state. Given, bond length of CO = 112.8 pm and 1 a.m.u.
= 1.66 × 10−27 kg.
Solution: The energy of J th level of a rigid rotor is given bye
h2
EJ = J(J + 1),
8π 2 µr2
where µ = reduced mass, r = length and other terms have their usual signif-
icance.
For CO,
mC mO
µ=
mC + mO
12 × 1.66 × 10−27 × 16 × 1.66 × 10−27
=
(12 + 16) × 1.66 × 10−27
= 6.857 × 1.66 × 10−27 kg
112
Given r = 112.8 × 10−12 m. Therefore, the frequency of light absorbed when
a CO molecule makes a transition from the rotational ground state (J = 0)
to the first excited state (J = 1) is
E1 − E0
ν=
h
h
= 2 2 ×2
8π µrCO
6.626 × 10−34
= −27 −12 −12
Sec−1
16.0 × 3.14 × 3.14 × 6.857 × 1.66 × 10 × 112.8 × 10 × 112.8 × 10
= 2.9 × 1010 Sec−1
11) What is an orbital? what does the following diagram represent for a
pz orbital? Solution: An orbital is a three-dimensional space around the
+ +
- -
nucleus, where the probability of finding an electron is maximum.

The given diagram represents the spherical harmonics for the pz orbital. The
signs ‘+’ and ‘-’ represents the two phases of the wavefunction of pz orbitals
and hence it shows that the two lobes of pz orbital have different phases.
2009: 1) State Heisenberg’s uncertainty principle for position and momentum.

The speed of an electron in x-direction is measured as vx = 300m/sec with an
uncertainty of 0.01%. What would be uncertainties in position ∆x and ∆y,
when position is measured simultaneously with speed? Comment on your
result. Given that me = 9.1 × 10−31 kg. x- and y-directions are mutually
perpendicular.
Solution: (i) Heisenberg uncertainty principle It states that “It is impossi-
ble to determine both the exact position and exact momentum of a quantum
system, at the same time, not even theoretically.”
(ii) The relation between the uncertainty in linear momentum and position
of a particle along x-axis is given by
h
∆px ∆x ≥
4π
Given,
0.01
∆vx = × 300
100
= 0.01m.sec−1
=⇒ ∆px = m∆vx
= 9.1 × 10−31 kg × 0.01m.sec−1
= 9.1 × 10−33 kg.m.sec−1
113
Thus,
h
∆x ≥
4π∆px
6.626 × 10−34 J.sec
≥
4 × 3.14 × 9.1 × 10−33 kg.m.sec−1
≥ 0.0579 m
Since the two operators ŷ and p̂x commute with each other because the two
directions x and y are independent of each other (orthogonal), there exist
no uncertainty relation between position along y axis and momentum along
x axis. Thus, whatever may be the uncertainty in px , the measurement of
particles position along y axis will not be affected and hence the corresponding
uncertainty in y will be zero.
2) Evaluate the commutator x̂2 , p̂x

Solution:
2
x̂ , p̂x ψ = x̂2 p̂x ψ − p̂x x̂2 ψ
dψ d
= −i~x2 + i~ (x2 ψ)
dx dx
dψ dψ
= −i~x2 + i~x2 + i~ψ × 2x
dx dx
= 2ix~ψ
2
x̂ , p̂x = 2ix~
3) (i) What is Compton effect? (ii) Determine the scattering angle, for which
the shift in wavelength would be maximum. (iii) Find the maximum kinetic
energy of recoil electrons when x-rays of wavelength 12.0pm are scattered
from a target.
Solution: For part (i) and (ii), please see question 2 of year 2015.
(iii) The kinetic energy of recoil electron in Compton scattering is given by

1 1
K.E = hc − ,
λ λ0
where λ and λ0 are the wavelength of the incident and scattered photons
respectively. We know,
h
λ0 − λ = (1 − cosθ) ,
m0 c
where θ is the angle of scattering, m0 is the rest mass of the electron. So,
the kinetic energy of recoil electron will be maximum when cosθ = −1 =⇒
λ0 − λ = m2h0 c . Thus the maximum kinetic energy of the recoil electron is
hc(λ0 − λ)
K.E =
λ0 λ
hc × m2h0 c
=
2h
m0 c + λ λ
2h2
= 2h

c + m0 λ λ
2
2 × 6.626 × 10−34
= 2×6.626×10−34

3×108 + 9.1 × 10−31 × 12 × 10−12 × 12 × 10−12
87.8077 × 10−68
= = 4.771 × 10−15 J
184.044 × 10−54
114
4) Explain why p-orbitals are often represented as px , py and pz , instead of
p0 , p+1 and p−1 .
2 d2
5) Determine the eigenvalue when Ψ(x) = Axe−x /2 and Ĥ = − dx 2
2 + x . Give
the schematic plot of Ψ(x) and |Ψ(x)|2 versus displacement in x-direction.

Solution: For part (i) please see question 6(i) of year 2011.
(ii)
��
�
� �
6) Calculate the probability of finding a free particle confined in a 1D box of

length L within the region from L/4 to 3L/4.
Solution: The required probability is
3L/4
Z r !2
2 nπx
P = sin dx
L L
L/4
3L/4
Z
1 2nπx
= 1 − cos dx
L L
L/4
3L/4
1 L 2nπx
= x− sin
L 2nπ L L/4
3 1 3nπ 1 1 nπ
= − sin − + sin
4 2nπ 2 4 2nπ 2
1 1 nπ 3nπ
= + sin − sin
2 2nπ 2 2
7) What is the concept associated with de Broglie hypothesis? Starting from

this hypothesis, arrive at the energy expression for a free particle confined in
a 1D box.
Solution: The concept associated with the de Broglie hypothesis is wave-
particle duality. That means all the materials also have wave-like properties.
The wavelength of the wave associated with a particle of mass having mo-
mentum p is given by
h
λ=
p
For a particle confined in a 1D box of length L, the length of the box should
be an integral multiple of the wavelength of the associated wave. Otherwise,
the particle will be annihilated due to the destructive interference of the
associated waves. Thus,
L = nλ
h
L = n Using the above relation.
p
If there is a fixed potential V inside the box and E be the energy of the
115
p
particle then, p = 2m(E − V ). Thus
nh
L=p
2m(E − V )
2 n2 h2
L =
2m(E − V )
n2 h2
E= +V
2mL2
8) Hydrogen atoms 1s wavefunction is given by,
1/2
1 1
Ψ=√ e−r/a0 .
π a0
Determine the most probable value of r in this state.

2008: 1) Determine stating reasons whether each of the following functions is ac-
ceptable or not as a state function over the indicated intervals: (i) e−|x| (−∞ ≤
x ≤ ∞), (ii) sinx(0 ≤ x ≤ ∞).
Solution: (i) Please see question 1 of year 2013.
(ii) sinx is periodic function. It’s values lies between -1 and +1. In the range
(0 ≤ x ≤ ∞) it is finite, continuous, single-valued and square integrable. So,
it is an acceptable state function over the indicated interval.
2) An electron is confined in a 1D box of length L. What should be the length
of the box to make its zero-point energy equal to its rest mass energy (me c2 )?
Explain the result in terms of the Compton wavelength.
Solution: The energy of an electron in a 1D box of length l is given by
n2 h2
E=
8me L2
If this energy equals the rest mass energy of the electron then,
2 n2 h2
me c =
8me L2
h n
L= √
me c 2 2
Thus, if the length of the box is √n2 times the Compton wavelength of an
electron then the energy will hbe equal
i to the2 rest mass of the electron.
2
~ d
3) Evaluate the commutator x̂, Ĥ . Ĥ = 2m dx2 + V (x)
Solution:
h i
x̂, Ĥ ψ = x̂Ĥψ − Ĥ x̂ψ
2 2 2 2
~ d ~ d
=x + V (x) ψ − + V (x) xψ
2m dx2 2m dx2
~2 x d2 ψ ~2 d2
= +xV (x)ψ − (xψ) −
xV (x)ψ

2m dx 2 2m dx 2
~ x d ψ ~ x d ψ ~2 ψ d2 x
2 2 2 2
= − −
2m dx2 2m dx2 2m dx2
=0
116
αx2
4) Show that Ψ = ( απ )1/4 e− 2 is an√energy eigenfunction of the simple har-
monic oscillator in 1D. Given, α = ~kµ . Terms have their usual significance.
Solution: The hamiltonian of the simple harmonic oscillator in 1D is
s
2 2
~ d 1 2 2 k
Ĥ = − + µω x , where ω = and k is the force constant
2µ dx2 2 µ
Thus,
~2 d2

1 2 2 α 1/4 − αx2
ĤΨ = − + µω x e 2
2µ dx2 2 π
~2 α 1/4

d 2αx − αx2 1 2 2 α 1/4 − αx2
=− × × − e 2 + µω x × e 2
2µ π dx 2 2 π
~2 α 1/4

2αx − αx2 − αx2 1 2 2 α 1/4 − αx
=− × × (−α) × x − e 2 + e 2 + µω x × e 2
2µ π 2 2 π
2 2 2
~2 α 1 2 2 α 1/4 − αx2

~αx
= − + + µω x e 2
2µ 2µ 2 π
Putting the expressions for α and ω,

( s )
2
kx ~ k 1 2 α 1/4 − αx2
ĤΨ = − + + kx e 2
2 2 µ 2 π
s
1 k
= ~ ψ
2 µ
Thus, Ψ is an eigenfunction
q of Ĥ for a simple harmonic oscillator and the
eigenvalue is 21 ~ µk .
5) The lifetime of an excited state is 109 sec. Calculate the uncertainty in the
energy of this state.
Solution: According to Heisenberg uncertainty principle, the uncertainty in
energy (∆E) of a state and its lifetime (τ ) is given by
h
∆Eτ ≥
4π
6.626 × 10−34
∆E ≥ J
4 × 3.14 × 109
∆E ≥ 0.5275 × 10−25 J
6) Apply de Broglie’s hypothesis to arrive at the Bohr’s quantization rule.

7) Benzene may be regarded as a 4.0Åsquare box containing 6 pi electrons.
Find the expression for energy of the ground state of the system. Calculate the
minimum energy required to promote one electron to the lowest unoccupied
energy level.
Solution: Please see question 3 of year h 2013.
i
8) Two operators Â, B̂ are related as Â, B̂ = 0. How accurately can one
measure the physical property corresponding to Â, for a system in eigenstate
of B̂? Justify your answer. Assume the eigenstate as non-degenerate.h i
Solution: Let ΨB be an eigenfunction of B̂ with eigenvalue b. Since Â, B̂ =
117
0, this means ÂB̂ − B̂ Â = 0 =⇒ ÂB̂ = B̂ Â. Thus, if the system is in ΨB ,
we can write
B̂ ÂΨB = ÂB̂ΨB
= ÂbΨB
= b × ÂΨB
This indicates ÂΨB is an eigenfunction of B, which is possible only when

ÂΨ
h B= i constant × ΨB , which means ΨB is also an eigenfunction of Â. So, if
Â, B̂ = 0, then one can measure the physical property corresponding to Â
with 100% accuracy for a system in eigenstate of B̂.
9) A normalized wavefunction F (φ) = Aeimφ is defined in the range 0 ≤ φ ≤
2π. Find A. Using the conditions for acceptability of a wavefunction, obtain
the allowed values that the quantum number ‘m’ may take up.
Solution: Applying normalization condition,
Z2π
F ∗ (φ)F (φ)dφ = 1
0
Z2π
A∗ e−imφ Aeimφ dφ = 1
0
Z2π
|A|2 dφ = 1
0
|A|2 2φ = 1
1
|A| = √
2π
Since, this is an azimuthal equation after each 2π rotation the function
should return to its initial value. Thus, the condition of acceptability for
the given wavefunction is F (φ) = F (φ + 2π). This is possible only when
m = 0, ±1, ±2, · · · .
10) Define radial distribution function and state its significance. Plot ra-
dial distribution function corresponding to the following wavefunction against
r/a0 : Ψ = A(2a0 − r)e−r/2a0 . Terms have their usual significance.
2007: 1) (i) Show that hpi is zero for all the stationary states of a particle in a 1D
box of length L. (ii) Does it mean that the particle is at rest? Explain.
Solution: For part (i) Please see question 6 of year 2013.
(ii) The zero expectation value of linear momentum, hpi means the average
value of linear momentum of the particle is zero. It does not mean that
the particle is at rest. Particle in a box has equal probability of moving
towards the left or right sided wall and hence has equal values of left and
right momentum. So, on average, the positive and negative (left and right
values) momentum cancel out each other and the average becomes zero.
2) Determine whether each of the following functions is normalizable or not
over the indicated intervals: (i) ex (0, ∞), (ii) sinx(0, 2π). Normalize the
function that can be normalized.
118
Solution: (i)
Z∞
∞
ex × ex dx = 2 e2x 0 = ∞
0
So, ex is not normalizable in the interval (0, ∞)

(ii)
Z2π Z2π
1
sinx × sinxdx = (1 − cos2x) dx
2
0 0
2π
1 1
= x − sin2x
2 2 0
1
= [2π − 0 − 0 + 0]
2
1
=
2
So, the function sinx is normalizable in the interval (0, 2π).
3) A photon of momentum 5.33 × 10−22 g.cm.sec−1 is required to excite the
electron in a H-atom from the ground state to the first excited state. Use
this information to find the ionization energy of the H-atom.
Solution: Since E = hc h
λ and from de Broglie relation we know p = λ . This
means E = pc. Thus energy of the photon is 5.33 × 10−22 × 3 × 1010 erg. This
is the energy gap between the ground and first excited states.
The energy required to excite an electron from mth state to nth state, in
H-atom, is given by
me4

1 1
Emn = 2 2 −
80 h n2 m2
For ground state (m = 1) to first excited state (n = 2) transition, in H-atom,
is given by
3 me4
E12 = − × 2 2
4 80 h
Now, ionization energy (IE) will be a transition from ground state (m = 1)
to n = ∞ state. Thus
me4
E1∞ = (0 − 1)
820 h2
4
IE = E12 , Using the above relation.
3
4
IE = × 5.33 × 10−22 × 3 × 1010 erg = 21.32 × 10−12 erg.
3
4) For the ground state of the H-atom, find the most probable distance of the
electron from the nucleus, give
1
Ψ1s = 3/2
e−r/a0
π 1/2 a0
5) Express mathematically the Planck’s distribution law for black-body radi-
ation and show that under a particular condition it reduces to the Rayleigh-
Jeans law.
119
Solution: Planck’s distribution law for black-body radiation is given by,
2hc2 1
Bλ = 5 hc ,
λ e λkT − 1
hc
where terms have their usual meanings. In longer wavelength region, e λkT ∼
hc
1 + λkT . Thus,
2hc2 1
Bλ = 5 hc
λ 1 + λkT −1
2hc2 λkT
= 5 ×
λ hc
2ckT
= , which is Rayleigh-Jeans law.
λ4
6) Show that, in a rectangular box with infinitely high potential walls and of
sides a = L and b = 2L, there is a degeneracy between the states (1,4) and
(2,2). Write down the wavefunction for the state (1,0) and comment on the
result.
7) How can you use kinetic energy of photo-electron vs frequency plot in
photoelectric experiments to distinguish between two metals.
Solution: The relation between kinetic energy (T ) of photo-electron and the
frequency (ν) of light used is T = hν − W0 , where h = Planck’s constant and
W0 = work function of the metal. So a plot of T vs nu will be a straight
line having slope h (which is a constant) and an y-intercept of −W0 . Since
work function W0 is a characteristics of a metal, two different metals will
have different values of W0 i.e. different values of y-intercept. Thus, for two
metals the plot will look like
��
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8) The work function for metallic Cesium is 2.14 eV. Calculate the kinetic
energy of the electrons ejected by light of wavelength 300 nm.
Solution:Einstein’s equation of photoelectric effect is given by: T = hc
λ −W,
where T = kinetic energy of the electron emitted, λ = wavelength of light
used, W = work function of the metal, h and c are the Planck’s constant
and speed of light in vacuum respectively. Given, λ = 300 × 10−9 m, W =
2.14eV = 2.14 × 1.602 × 10−19 J. Thus we can write
6.626 × 10−34 J.Sec × 3 × 108 m.sec−1
T = −9
− 2.14 × 1.602 × 10−19 J
300 × 10 m
= 6.626 × 10 − 3.428 × 10−19 J
−19
= 3.198 × 10−19 J
120
h i
9) Given [x̂, p̂x ] = i~, evaluate Â and x̂, Â , where x̂, p̂2x = Â.

Solution: Given, [x̂, p̂x ] = i~ =⇒ x̂p̂x − p̂x x̂ = i~
A = x̂, p̂2x

= x̂p̂2x − p̂2x x̂
= x̂p̂x p̂x − p̂x p̂x x̂
= x̂p̂x p̂x − p̂x (x̂p̂x − i~)
= x̂p̂x p̂x − p̂x x̂p̂x + i~p̂x
= (x̂p̂x − p̂x x̂) p̂x + i~p̂x
= i~p̂x + i~p̂x
= 2i~p̂x
Thus,
h i
x̂, Â = x̂Â − Âx̂
= 2i~x̂p̂x − 2i~p̂x x̂
= 2i~ (x̂p̂x − p̂x x̂)
= 2i~ × i~ = −2~2
10) Explain whether “squaring” is a linear operation.

2006: 1) If Ψ(x) = N sin nπx

L for 0 ≤ x ≤ L, find N, where N is the normalization
constant.
Solution:
ZL
nπx 2
N sin dx = 1
L
0
ZL
N2

2nπx
1 − cos dx = 1
2 L
0
2
L
N L 2nπx
x− sin =1
2 2nπ L 0
N2
(L − 0 − 0 + 0) = 1
2 r
2
N=
L
2) State, with reasons, whether the functions Ψ(φ) = eiφ/2 and Ψ(x) = sin−1 x
are acceptable wavefunctions.
Solution: (i) Within the interval (0, 2π), Ψ(φ) is a finite, continuous and
single valued. It is also square integrable.
Z2π Z2π
Ψ∗ (φ)Ψ(φ)dφ = e−iφ/2 eiφ/2 dφ
0 0
Z2π
= dφ = 2π
0
121
Hence, Ψ(φ) is an acceptable wavefunction.
(ii) Please see question 2 of year 2012.
3) A micro-particle can be found anywhere with equal probability within a
length L. Find roughly its uncertainty in momentum. If the latter is the
minimum possible value of its momentum, find also the minimum kinetic
energy.
Solution: Since the probability of finding the particle at any point within
the length L is equal, the uncertainty in position will be ∆x = L. Therefore,
h
the uncertainty in momentum will be ∆p = 2πL .
Now, if the above uncertainty in momentum be minimum, then the minimum
kinetic energy will be
(∆p)2 h2
K.E.(min) = = 2
2m 8π mL2
4) The peak in the sun’s emitted energy occurs at about 480 nm. Estimate
the temperature of its surface assuming as a black-body like emitter. The
second radiation constant, C2 = hck = 1.439cm.K)
Solution:
2
5) A state Ψ = N e−ax satisfies an eigenvalue equation HΨ = EΨ with
d2 2
H = − dx 2 + x . Find possible values of a and eigenvalue E.
2
Solution: Since Ψ = N e−ax satisfies the eigenvalue equation HΨ = EΨ.
This means Ψ is normalized. Thus
Z+∞
2
N 2 e−2ax dx = 1
−∞
r
π
N2 =1
2a
1/4
2a
N=
π
Thus, a = π2 N 4 . Now, putting the expression of Ψ in the eigenvalue equation.
EΨ = ĤΨ
1/4
d2

2a 2
= − 2 +x 2
e−ax
dx π
1/4 o 2a 1/4
2a d n 2 2
=− −2axe−ax + x2 e−ax
π dx π
1/4
2a −ax2 2 −ax2
2
=2 a e − 2ax e + N x2 e−ax
π
1/4
2a 2
= 2a − 4a2 x2 + x2 e−ax

π
The eigenvalue should not depend upon the position. Therefore, −4a2 + 1 =
0 =⇒ a = ± 12 and hence E = ±1.
6) How is the de Broglie hypothesis used to obtain Bohr’s quantization rule
for H-atom?
Solution: Please
h see
i question 10 of year 2016.
2
d
7) Evaluate x2 , dx 2 without using [x, px ] = i~.
122
Solution:
2 2
d2

2 d 2d ψ 2

x , 2 ψ=x − x ψ
dx dx2 dx2
d2 ψ d2 ψ
= x2 2 − x2 2 − 2ψ
dx dx
= −2ψ
d2

=⇒ x2 , 2 = −2
dx
8) Explain whether the functions Ψ, −Ψ and 2iΨ represent the same state,
given that Ψ is real.
Solution: The expectation value of the property (P) of a system is given by,
H ∗
Ψ P̂ Ψdτ
hP i = H ∗
Ψ Ψdτ
If the wavefunction Ψ is multiplied by a constant k (real or imaginary) then

the property will not change. Thus
(kΨ)∗ P̂ kΨdτ k ∗ k Ψ∗ P̂ Ψdτ

H H H ∗
Ψ P̂ Ψdτ
H = H = H = hP i
(kΨ)∗ kΨdτ k ∗ k Ψ∗ Ψdτ Ψ∗ Ψdτ
If k = −1, the wavefunction is −Ψ and if k = 2i, the wavefunction is 2iΨ.

Thus, all the three wavefunctions Ψ, −Ψ and 2iΨ represent the same state.
9) Calculate hx2 i for a particle in a 1D box with 0 ≤ x ≤ L and comment on
its value as n → ∞.
Solution:
ZL r r
2 nπx 2 nπx
hx2 i = sin × x2 × sin dx
L L L L
0
ZL
1 2nπx
= 1 − cos x2 dx
L L
0
L L
1 x3 1 2xL2 2nπx x2 L L3

2nπx 2nπx
= − sin − cos + 3 3 cos
L 3 0 L 4n2 π 2 L 2nπ L 4n π L 0
L2 L2 L2 L2
= −0+ cos2nπ − 3 3 cos2nπ + 0 − 0 + 3 3
3 2nπ 4n π 4n π
2 2 2 2
L L L L
= + 3 3+ − 3 3 cos2nπ
3 4n π 2nπ 4n π
When n → ∞, all the terms except the first one will → 0. Thus as n → ∞,
2
hx2 i → L3 .
10) Identify the following hydrogenic orbitals with given radial parts as (i)
N1 (β2 − r)e−α2 r and (ii) N2 e−α3 r , where Ni , αi and βi are constants. Explain
your answer using plots of the orbitals.
Solution: Radial distribution plots of the two given wavefunctions are shown
below. Since the wavefunction (i) N1 (β2 − r)e−α2 r has one node (except at
r = 0 and r = ∞, it represents a 2s orbital. Similarly, since the wavefunction
(ii) N2 e−α3 r has no node (except at r = 0 and r = ∞, it represents a 1s orbital.
123
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��
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2005: 1) Indicate and explain the salient features of the photoelectric effect.
Solution: Please see relevant section of the text (Section: ??).
2) Evaluate [x̂n , p̂x ]
3) Show that Ψi (x) and Ψj (x) representing the wavefunctions corresponding
to two different sates of a particle confined in a 1D box are orthogonal.
Solution:
ZL ZL r r
2 iπx 2 jπx
Ψi Ψj dx = sin sin dx
L L L L
0 0
ZL
1 iπx jπx
= 2sin sin dx
L L L
0
ZL
(i − j)πx

1 (i + j)πx
= cos − cos dx
L L L
0

1 L L L L
= sinπ − sin0 − sin(i + j)π + sin0
L (i − j)π (i − j)π (i + j)π (i + j)
= 0, as both i and j are integers.
Thus, the two states are orthogonal to each other.

4) Write down time independent Schrödinger equation of a 1D harmonic os-
cillator. Comment on its zero-point energy.
Solution: Time independent Schrödinger equation of a 1D harmonic oscil-
lator is
~2 d2

1 2 1
− + kx Ψ(x) = (v + )~ωΨ(x),
2m dx2 2 2
where k =force constant, v = vibrational quantum number and ω is angular
frequency of oscillation.
The zero-point energy of the oscillator corresponds to the value of energy for
the quantum number v = 0. Thus, zero-point energy is 12 ~ω and non-zero.
5) From the probability density of 1s electron, show that the most probable
distance of the electron from the nucleus is equal to Bohr radius. Given
1
Ψ1s = 1/2
e−r/a0
(πa30 )
6) Find the de Broglie wavelength of electrons that have been accelerated from
124
rest through a potential difference of 1.00 KV. h = 6.626 × 10−34 J.Sec; me =
9.11 × 10−31 kg.
Solution: de Broglie relation is
h
λ= ,
p
where p = momentum of the electron. If the electron is accelerated from rest
through a potential difference of 1.00kV, then the enegy of the electron will
be = 1.602 × 10−19 × 1000 J. √
The√ momentum of the electron will be p = 2mE
= 2 × 9.11 × 10−31 × 1.602 × 10−19 × 1000 = 1.708 × 10−23 kg.m.sec−1
Therefore, the de Broglie wavelength of the electron will be
6.626×10−34 −11
λ = 1.708×10 −23 = 3.879 × 10 m
7) What is meant by degeneracy? Find the quantum numbers associated with
the energy level 17h2 /8ma2 of a particle in a cubical box and hence indicate
the degree of degeneracy.
Solution: When two different states corresponding to different values of
quantum numbers, possess the same energy, the two states are called degen-
erate and this phenomenon is called degeneracy.
The quantum numbers associated with the energy level 17h2 /8ma2 of a par-
ticle in a cubical box are : (nx = 2, ny = 2, nz = 3), (nx = 2, ny = 3, nz =
2), (nx = 3, ny = 2, nz = 2). So, degree of degeneracy is 3.
8) Solve the Schrödinger equation for a particle in a 1D box and find the
expressions for the wavefunction and energy.
Solution: Please see the relevant text (section: ??).
9) Calculate the frequency of radiation emitted when a linear harmonic os-
cillator of frequency 6.0 × 1013 sec−1 goes from n = 2 to n = 1 state.
Solution: The frequency of radiation emitted by a linear harmonic oscillator
(of frequency ω) when it goes from state v 0 to v is given by

1 1 1
ν= (v + )hω − (v + )hω = (v 0 − v)ω
0
h 2 2
In our case, v 0 = 2 and v = 1. Thus
ν = (v 0 − v)ω = ω = 6.0 × 1013 sec−1
10) Calculate the probability that an electron in the ground state of a H-atom
will be found within one Bohr radius of the nucleus. Given
1
Ψ1s = 1/2
e−r/a0
(πa30 )
2004: 1) Sketch the energy distribution curves of the radiation emitted from a black
body at two different temperatures and point out two characteristic features
of the energy distribution.
Solution: Please see relevant section in the text. text to be added
2) Derive the expression for the energy of a particle in a 1D box using the de
Broglie formula.
3) Find the average position hxi of a particle constrained to lie in a 1D box
of length ‘a’ and with infinitely high potential walls in the lowest state E1 .
125
Would this location be a good place to seek the particle if it is in the next
energy level E2 ? Given
Znπ
2 n2 π 2
zsin zdz =
4
0
Solution: The average position hxi of a particle constrained to lie in a 1D
box of length ‘a’ and with infinitely high potential walls in any state n is
given by
Za r r
2 nπx 2 nπx
hxi = sin x sin dx
a a a a
0
Za
1 2nπx
= x 1 − cos dx
a a
0 2 a
1 x a2 2nπx ax 2nπx
= − 2 2 cos − sin
a 2 4n π a 2nπ a 0
2 2
a2

1 a a
= − 2 2 cos2nπ − 0 − 0 + 2 2 + 0
a 2 4n π 4n π
a a a
= − 2 2 cos2nπ + 2 2
2 4n π 4n π
For ground state n = 1 and cos2π = 1 and hence hxi = a2 . Thus, in ground
state the average position of a particle in a 1D box is at the middle of the
box. In the next energy level, n = 2, cos4π = 1 and hence hxi = a2 . Thus,
the average position of the particle in the next energy level (E2 ) is also at the
middle of the box.
ceptable or not as a wavefunction over the indicated intervals: (i) 1/x[0, ∞],
(ii) sin−1 x[−1, 1], (iii) e−x cosx[0, ∞].
Solution:For (i) and (ii) please see question 2 of year 2012.
For (iii), please see question 1 of year 2015.
5) Calculate the zero-point energy of a harmonic oscillator consisting of a
particle of mass 5.16 × 10−26 kg and force constant 285N.m−1 .
Solution: The zero-point energy of a harmonic oscillator consisting of a
particle of mass m and force constant k is given by
r
1 k
EZPE = ~
2 m
In our case, m = 5.16 × 10−26 kg, k = 285N.m−1 . Thus,
1 6.626 × 10−34
r
285
EZPE = × ×
2 2 × 3.14 5.16 × 10−26
= 3.9207 × 10−21 J
d2 2
R
6) Classify the following operators as linear or non-linear: dx 2 , ( ) , ( )dx, exp
d2
Solution: If φ and ψ be two functions and k be a constant then, (i) dx 2 (kφ +
d2 φ d2 ψ d 2
kψ) = k dx2 + k dx2 . Thus, dx 2 is a linear operator.
(ii) Please
R see question R2 or year 2011.
R R
(iii) (kφ + kψ)dx = k φdx + k ψdx. So, ( )dx is a linear operator.
(iv) exp(kφ + kψ) = exp(kφ) × exp(kψ) 6= k exp φ + k exp(ψ). So, exp is a
non-linear operator.
126
7) Evaluate the commutator x̂, p̂2x

8) Estimate the wavelength of light absorbed when a π electron of butadiene
is excited from the highest occupied energy level to the lowest vacant energy
level. For the sake of simplicity assume that the pi electrons of butadiene
move in a 1D box of length 7.0Å, me = 9.1 × 10−28 kg.
Solution: The required wavelength can be obtained from the relation
Elowest unoccupied level −Ehighest occupied level = hc
λ . For butadiene, highest occupied
level corresponds to n = 2 level and lowest unoccupied level corresponds to
n = 3 level. Thus, required wavelength is
hc
E3 − E2 =
λ
2
h hc
2
(9 − 4) =
8mL λ
8mcL2
λ=
5h 2
8 × 9.1 × 10−31 × 3 × 108 × 7.0 × 10−10
λ= m
5 × 6.626 × 10−34
λ = 323.018 × 10−9 m
9) For a simple harmonic oscillator: hxi = 0, hpi = 0, hx2 i = h(mk)−1/2 (v +
1/2) and hp2 i = h(mk)1/2 (v + 1/2), the terms have their usual significance.
Show that a simple harmonic oscillator obeys the uncertainty principle by
computing ∆x and ∆p.
Solution:
p
s
h
= √ (v + 1/2) − 0
mk
s
h
= √ (v + 1/2)
mk
p
∆p = hp2 i − hpi2
q
= h(mk)1/2 (v + 1/2) − 0
q
= h(mk)1/2 (v + 1/2)
Thus,
s
h
q
∆x∆p = √ (v + 1/2) × h(mk)1/2 (v + 1/2)
mk
1
= (v + )h
2
h
The minimum value of v is zero. So, ∆x∆p ≥ h or, ∆x∆p ≥ 4π . Thus,
Heisenberg uncertainty principle is obeyed by simple harmonic oscillator.
10) For the 1s state of the H-atom Ψ1s = b0 e−r/a0 .
(i) Find the normalization constant b0 .
(ii) Specify the values of n, l and m of 1s electron.
(iii) Evaluate the probability density for a 1s electron at the nucleus. Given
Z∞
n!
xn e−qx dx = n+1 , n > −1, q > 0
q
0
127
Solution: (i)
Z+∞
|Ψ1s |2 4πr2 dr = 1
0
Z+∞
4π|b0 |2 r2 e−2r/a0 dr = 1
0
2!a30
4π|b0 |2 =1
8
1
|b0 | = p 3
πa0
(ii) For 1s electron, n = 1, l = 0, m = 0.

(iii) Probability density at the nucleus is given by

∗ 1 −2r/a0
1
Ψ1s Ψ1s |r=0 = e =
πa30
r=0 πa30
2003: 1) Indicate and explain the salient features of the photoelectric effect.
Solution: Please see relevant text (section ??).
2) State the conditions of “acceptability of wave function” in quantum me-
chanics with explanation. Illustrate the function e−x is acceptable wavefunc-
tion within the range (0, ∞).
Solution: A wavefunction is acceptable if it satisfies the following conditions:
(i) It is finite, single valued and continuous function within the boundary of
the system.
(ii) It’s partial first derivatives with respect to the Cartesian coordinates of
each particle of the system should be continuous.
(iii) It should be quadratically integrable.
(iv) It should satisfy the boundary condition of the system.
(v) For fermions, it should be antisymmetric with respect to the exchange of
position of any two fermions in the system.
e−x is a single valued, continuous and finite function in the range (0, ∞). The
derivative of e−x with respect to x is −e−x , which is also continuous over the
indicated interval. The function is also square integrable, as shown below
Z∞
1 −2x ∞ 1 −∞ 1 1
e−2x dx = − 0

e 0
= − e − e = − (0 − 1) =
2 2 2 2
0
Hence, e−x is an acceptable wavefunction within the range (0, ∞).

3) If Ψ1 and Ψ2 are two eigenfunctions with same eigenvalue E, prove that any
linear combination C1 Ψ1 +C2 Ψ2 is also an eigenfunction with same eigenvalue.
4) The eigenfunction for a particle
1/2
2 mπx
Ψm (x) = sin , m = 1, 2, 3, · · ·
L L
where x is defined within 0 ≤ x ≤ L. Show that these eigenfunctions are
orthogonal.
5) The wavefunction for the state of lowest energy of a 1D harmonic oscillator
128
2 1
is Ψ = Ae−Bx , where A is a normalization constant and B = 2h (µk)1/2 . The
potential energy for the oscillator, V (x) = 21 kx2 . Write the Schrödinger
equation for the system and qhence show that the total energy E of the lowest
state is 12 hν, where ν = 2π
1 k h
µ and ~ = 2π .
Solution: The Hamiltonian for a simple harmonic oscillator is
h2 d2 1
Ĥ = − 2 2
+ kx2 ,
8π m dx 2
where k is the force constant. Let us apply this hamiltonian on the given
2
wavefunction Ψ(x) = Ae−Bx .
h2 d2 Ψ(x) 1 2
ĤΨ(x) = − 2 + kx Ψ(x)
8π µ dx2 2
2 2
h d −Bx2 1 2 −Bx2
= −A 2 e + kx Ae
8π µ dx2 2
2
h d n
−Bx2
o 1 2
= −A 2 −2Bxe + kx2 Ae−Bx
8π µ dx 2
2 n
h −Bx2

−Bx2
o 1 2
= 2AB 2 x −2Bxe +e + kx2 Ae−Bx
8π µ 2
2 2
h 2 h 2 1 2
= −4AB 2 2 x2 e−Bx + 2AB 2 e−Bx + kx2 Ae−Bx
8π µ 8π µ 2
p
Since B = (µk)/2~ =⇒ B 2 = µπ 2 k/h2 . Putting these in the above
equation,
√
h2 π 2 µk 2 −Bx2 π µk h2 −Bx2 1 2 −Bx2
ĤΨ(x) = −4A 2 xe + 2A e + kx Ae
8π µ h2 h 8π 2 µ 2
s
1 2 h k −Bx2 1 2 −Bx2
= −A kx2 e−Bx + A e + kx Ae
2 4π µ 2
s
h k −Bx2
= Ae
4π µ
s
1 2 1 k
= hνAe−Bx , where, ν = = frequency of oscillation.
2 2π µ
q
Thus, the total energy E of the lowest state is 2 hν, where ν = 2π mk .
1 1
6) (i) Write the Schrödinger equation for a particle in 1D box of length L

having V = 0 inside the box and V = ∞ at the walls and outside the box.
Find the expression for the energy and wavefunction of the particle.
(ii) Why is the value of n = 0 of the quantum number not permitted?
(iii) Find the average value of px , hpx i for n = 1 state. Comment on your
result.
(iv) If the particle is in its ground state, what is the probability of finding
the particle in the range L/3 to 2L/3?
Solution: (i) Let, the box lies between x = 0 and x = L along the x−axis
and m be the mass of the particle. Then, the required Schrödinger equation
will be
h2 d2 ψ
− 2 = Eψ, 0 < x < L
8π m dx2
This is a standard second order differential equation of the form
d2 ψ
2
+ k 2 ψ = 0,
dx
129
q
8π 2 mE
where k = h2 . It has a standard solution, given by
ψ = Acoskx + Bsinkx
A and B are constants, which can be determined by applying boundary con-

ditions. The boundary conditions are
(i)At x = 0, ψ = 0
And (ii)At x = L, ψ = 0
These boundary conditions give,
0=A
0 = AcoskL + BsinkL
Since, B cannot be equal to zero (otherwise there will not be any wavefunc-
tion). So,
sinkL = 0
=⇒ kL = nπ, where n is an integer.
Putting the expression for k, we get

r
8π 2 mE
L = nπ
h2
8π 2 mE 2
2
L = n2 π 2
h
n2 h2
E=
8mL2
This is the required expression for energy. (ii) Note that, the value of n can-
not be zero, as this will gives a ψ = 0. q
(iii) The wavefunction of the particle in ground state is ψ = L2 sin πx
L . There-
fore, the probability of finding the particle in the range L/3 to 2L/3 is given
by
2L/3
Z r !2 2L/3
Z
2 πx 1 2πx
sin dx = 1 − cos dx
L L L L
L/3 L/3
2L/3
1 L 2πx
= x − sin
L 2π L L/3

1 2L L 4π L L 2π
= − sin − + sin
L 3 2π 3 3 2π 3
√ √
1 1 3 3
= + ( + ) = 0.609
3 2π 2 2
7) A cubic box with each side measuring 10Å(with zero potential inside and
infinite potential outside) contains a system of 4 quantum particles. Find the
degeneracy of the lowest energy state of the system.
Solution: The energy of a particle in a cubic box is given by
h2
E(nx , ny , nz ) = (n2x + n2y + n2z )
8mL2
130
The lowest energy level corresponds to the quantum number (1, 1, 1). This
energy level is non-degenerate and hence has degeneracy = 1.
8) The wavefunction for a 1s orbital for a H-atom is
1
Ψ1s = 1/2
e−r/a0
(πa30 )
where a0 = Bohr radius. Depict graphically the plots of (i) Ψ against r and
(ii) 4πr2 Ψ2 against r. Explain the graph. Find the most probable value of r
in the SI unit.
Solution: The plot (i) Ψ against r and (ii) 4πr2 Ψ2 against r are shown below.
��
�
� �
Ψ vs r plot represents that the wavefunction gradually decreases with the in-
crease in distance from the nucleus. After a certain distance the wavefunction
becomes almost zero.
4πr2 Ψ2 is the radial distribution function and it represents the probability of
finding the electron anywhere on the surface of a sphere located at a distance
r from the nucleus. We see that the plot at first increases with the increase
in distance and it reaches the maximum point at r = a0 and then with the
further increase in distance from the nucleus the plot falls rapidly. This plot
represents that the most probable location of an electron in 1s orbital is at
the Bohr radius distance = 0.529 × 10−10 m.
2002: 1) Write down the (i) Stefan-Boltzmann law, (ii) Wien’s displacement law
indicating the quantities involved.
Solution: (i) Stefan-Boltzmann law: The total energy emitted from a black-
body is proportional to the fourth power of thermodynamic temperature of
the surface. Thus, E = σT 4 , where E = total heat energy emitted, σ =
Stefan’s constant and T = temperature of blackbody in Kelvin.
(ii) Wien’s displacement law: The radiant energy emitted by a blackbody at
a particular temperature is maximum for a wavelength that is inversely pro-
portional to the temperature of the blackbody. Thus, λmax ∝ T1 , where λmax
represents the wavelength at which the radiant energy emitted by a black-
body at temperature T is maximum.
ceptable or not as a wavefunction over the indicated intervals: (i) e−x (0, ∞),
(ii) e−x (−∞, ∞), (iii) sin−1 x(−1, 1), (iv) e−|x| (−∞, ∞).
Solution: (i) Please see question 2 of year 2002.
(ii) e−x becomes infinite at x = −∞. Thus, it is not an acceptable wavefunc-
tion in the interval (−∞, ∞)
(iii) Please see question 1 of year 2015.
(iv) Please see question 1 of year 2013.
3) The wavefunction of a particle of mass m which moves in one dimension
between x = a and x = b is Ψ = Ax , where A is a normalization constant. (i)
ab
calculate A, (ii) show that x̄ = a−b ln ab , where x̄ represents the average value
131
of x.
Solution: (i) Applying normalization condition,
Zb
A
| |2 dx = 1
x
a
b
1
|A|2 − =1
x a

2 1 1
|A| − + =1
b a
r
ab
|A| =
b−a
(ii) Calculating x̄
Zb
x̄ = Ψ∗ xΨdx
a
Zb r r
ab 1 ab 1
= ×x× dx
b − ax b − ax
a
Zb
ab 1
= dx
b−a x
a
ab
= [lnx]ba
b−a
ab
= (lnb − lna)
b−a
ab b
= ln
b−a a
4) Calculate the de Broglie wavelength of an electron travelling at 1% of the
speed of light. (me = 9.1 × 10−28 g).
Solution: The required de Broglie wavelength is λ = mhe v , where me =
9.1 × 10−31 kg, v = 0.01 × 3 × 108 m.sec−1 and h = 6.626 × 10−34 J.sec.
Putting all these values, we get
6.626 × 10−34
λ=
9.1 × 10−31 × 0.01 × 3 × 108
= 0.2427 × 10−9 m
5) Calculate the frequency of radiation emitted when a linear harmonic os-

cillator of frequency 6.0 × 1013 sec−1 goes from v = 8 to v = 7 state.
6) For a particle of mass m in a cubic box of length L with zero potential
inside and infinite potential on the walls and outside,
(i) write down the expressions for the wavefunctions and the energy.
(ii) What is the degeneracy of the level that has an energy three times that
of the lowest level?
Solution: (i) Wavefunctions:
r
Ψ(nx , ny , nz ) = sin sin sin
L3 L L L
132
Energies:
h2
E(nx , ny , nz ) = n2x + n2y + n2z
8mL2
2
3h
(ii) The lowest energy level has energy E(1, 1, 1) = 8mL 2 . The energy of the
9h2
level which has three times the energy of lowest energy level is E = 8mL 2.
This energy corresponds to the following combinations of quantum numbers:

(1, 2, 2), (2, 1, 2), (2, 2, 1). Thus, this energy level is three fold degenerate.
7) Sketch |Ψ|2 for n = 1 and n = 2 states of a particle in a 1D box of length
L and indicate the most likely locations of the particle in the state n = 1 and
n = 2.
Solution:
most probable
location for most probable most probable
n=2 location for location for
n=1 n=2
8) Consider a particle constrained to move in a 2D box. Determine [x̂, p̂y ]

and interpret the result.
Solution: The wavefunction for a particle constrained in a 2D box is given
by
2 nx πx ny πy
Ψ(x, y) = p sin sin
Lx Ly Lx Ly
Thus,
[x̂, p̂y ]Ψ(x, y) = x̂p̂y Ψ(x, y) − p̂y x̂Ψ(x, y)

( )
d 2 nx πx ny πy d 2 nx πx ny πy
= −i~x p sin sin + i~ xp sin sin
dy Lx Ly Lx Ly dy Lx Ly Lx Ly

2i~ nx πx ny π ny πy nx πx ny π ny πy
=p −xsin × sin + xsin × sin
Lx Ly Lx Ly Ly Lx Ly Ly
=0
Thus, for a particle constrained to move in a 2D box, [x̂, p̂y ] = 0. The two
operators commute. This means the position of the particle along x−axis
and it’s momentum along y−axis can be determined simultaneously and ac-
curately. This is obvious. Because the two Cartesian axes x and y are orthog-
onal to each other and hence independent. This makes the properties along
each axes independent of each other. That’s why, all the one-dimensional
operators along different Cartesian axes commute with each other.
d2
9) Is the function Ae−ax an eigenfunction of the operator dx 2 ? If so, what is
the eigenvalue?
Solution:
d2 −ax d
2
Ae = A (−ae−ax ) = a2 Ae−ax
dx dx
2
d
Thus, Ae−ax is an eigenfunction of the operator dx 2
2 . The eigenvalue is a .
10) The radial wavefunction for 2s orbital of a H-atom is given by the following
expression:
r r
R2,0 = N 2 − e− 2a0
a0
133
where N is a constant.
(i) Determine the number and location of node(s) in the 2s wavefunction.
(ii) Write down the expression for the radial distribution function of a 2s
electron and sketch the radial distribution curve.
Solution: (i) The function

r r
R2,0 = N 2 − e− 2a0
a0
is zero at r = 2a0 and r = −∞. Since r = −∞ is not considered as a node,

the 2s orbital has one node. 2 r
(ii) Radial distribution function of a 2s orbital 4πr R2,0 = 4πN r 2 − a0 e− a0 .
2 2 2 2 r
The corresponding sketch is

��
2001: 1) What is photoelectric effect? How can the important features be explained?
Solution: Please see relevant section in the text (section ??).
2) Calculate the minimum uncertainty in position for an automobile of mass
500kg moving with speed 50 ± 0.001km.hr−1 . Comment on the result. h =
6.627 × 10−34 J.Sec.
Solution: The required minimum uncertainty in position is given by
h
∆xmin =
4πm∆v
6.626 × 10−34
=
4 × 3.14 × 500 × 0.001×1000
3600
−34
= 3.798 × 10 m.
3) Verify that the operator ∇2 is linear.

Solution:
2 ∂2 ∂2 ∂2
∇ = 2+ 2+ 2
∂x ∂y ∂z
If f and g be two functions of the Cartesian coordinates x, y, z and k be a
134
constant, then
∂2 ∂2 ∂2

2
∇ {k(f + g)} = + + {k(f + g)}
∂x2 ∂y 2 ∂z 2
∂2 ∂2 ∂2
= 2 k(f + g) + 2 k(f + g) + 2 k(f + g)
∂x ∂y ∂z
2 2
∂ ∂ ∂2
= k 2 (f + g) + k 2 (f + g) + k 2 (f + g)
∂x ∂y ∂z
∂2 ∂2 ∂2 ∂2 ∂2 ∂2
= k 2f + k 2g + k 2f + k 2g + k 2f + k 2g
∂x ∂x ∂y ∂y ∂z ∂z
2 2 2 2 2
∂ ∂ ∂ ∂ ∂ ∂2
= k 2f + k 2f + k 2f + k 2g + k 2g + k 2g
∂x ∂y ∂z ∂x ∂y ∂z
2
∂2 ∂2 ∂2 ∂2 ∂2

∂
=k + + f + k + + g
∂x2 ∂y 2 ∂z 2 ∂x2 ∂y 2 ∂z 2
= k∇2 f + k∇2 g
Thus, ∇2 is a linear operator.

4) State the postulate regarding dynamical variables of a particle in quan-
tum mechanics. From the definition of linear harmonic oscillator, obtain the
expression for the potential energy and hence construct the Hamiltonian op-
erator or the same.
Solution: There are three postulates regarding dynamical variables in quan-
tum mechanics.
(i) Every dynamical variable is represented by a corresponding hermitian op-
erator.
(ii) In an experiment, measuring a dynamical variable (A) of the system, the
only value that can be obtained will be the eigenvalue that satisfies Âψ = aψ,
where Â = hermitian operator corresponding to the dynamical variable (A),
ψ = wavefunction of the system and a = eigenvalue.
(iii) If a number of experiments are performed to measure the value of a
dynamical variable (A), then the average or the expectation value of the
dynamical variable associated with the operator Â is given by
+∞
ψ ∗ Âψdτ
R
−∞
hAi = +∞
R
ψ ∗ ψdτ
−∞
A linear harmonic oscillator is one which oscillates under a potential of 12 kx2 ,

where k = force constant. The Hamiltonian operator of a linear harmonic
oscillator is given by
h2 d2 1 2
Ĥ = − 2 + kx ,
8π µ dx2 2
where µ = reduced mass of the particle exhibiting harmonic oscillation.
5) What are the characteristic features of linear harmonic oscillator obeying
quantum mechanical laws.
Solution:
6) Solve the Schrödinger wave equation for a particle in a one dimensional
box and find the expression for eigenvalue and eigenfunction. Why is the
value of n = 0 of the quantum number not permitted?
7) What is normalization? Why is it necessary? What is its significance?
135
Solution: If ψ be the wavefunction of a particle in a particular state then
∗
R
ψ ψdτ represents the net probability of finding the particle anywhere
all space
in space. In principle, this probability should be equal to 1 (because the
probability should be somewhere). Even if ψ is a valid wavefunction of the
system, it may not give a total probability of 1. Normalization is the tech-
nique of scaling the wavefunction such that the total probability of finding
the particle anywhere in space becomes 1. Normalization does not change
the wavefunction, as in this process the wavefunction is multiplied by a con-
stant quantity. Normalization also rectifies the dimension (or unit) of the
wavefunction. Without normalization, any property calculated using the un-
normalized wavefunction will miss the exact value by a constant factor and
the calculated property will also suffer a dimensional error (unit related er-
ror).
8) Calculate the expectation value hxi for a particle in a 1D box of width L
and infinitely high potential at the walls with origin at the one end of the
box.
9) The wavefunction for a 1s orbital for a H-atom is
1
Ψ1s = p 3 e−r/a0 ,
πa0
where a0 is the Bohr radius. Depict graphically the plots of (i) Ψ against
r, (ii) Ψ2 against r and (iii) 4πrr Ψ2 against r. Explain with the help of the
above equation why the plots are different.
Solution: The required plots are
��
�
� �
��
1
Ψ1s = p 3 e−r/a0
πa0
1
Ψ21s = 3 e−2r/a0
πa0
4
4πr2 Ψ21s = 3 r2 e−2r/a0
a0
From the above three equations, it is obvious that Ψ1s is an exponentially
decaying function and so is reflected by its plot. Ψ21s is also an exponentially
decaying function but has larger exponent than Ψ1s and hence it falls off
rapidly as shown in figure. Finally, 4πr2 Ψ21s is the radial distribution function
136
and is a product of a parabolic function (r2 ) and an exponentially decaying
function. At smaller value of r the parabolic function dominates over the
exponential decay and hence the plot increases with the increase in r, at a
certain value the increasing trend of r2 is balanced by the exponential decay,
where the curve reaches a the peak. After that, the exponential decay starts
dominating the parabolic r2 and the hence the curve falls off till it becomes
zero at infinity.
2000: 1) Define a perfect black body. Write three characteristic features of intensity
distribution of radiation emitted by a black body.
Solution: (i) A perfect blackbody is a substance which absorbs all the radia-
tions incident on it and when it is heated it emits radiations of all wavelengths.
(ii) Three characteristic features of intensity distribution of radiation emitted
by a black body:
(a) The intensity distribution of radiation emitted by a blackbody is inde-
pendent of the material constitution of the blackbody and depends only on
its temperature.
(b) At any temperature, the radiant energy emitted at a particular wave-
length increases with the increase in wavelength and reaches a peak. The
wavelength corresponding to this peak is inversely proportional to the tem-
perature of the blackbody. With further increase in wavelength (at the same
temperature) the radiant energy emitted by the blackbody decreases.
(c) With the increase in temperature, the wavelength corresponding to the
peak in the blackbody radiation plot shifts to the lower value i.e. a blue shift
is observed.
2) If Ψ1 and Ψ2 are eigenfunctions of linear operator Â with the same eigen-
values a, show that any linear combination of Ψ1 and Ψ2 will also be an
eigenfunction of Â with the same eigenvalue.
3) Write down the Schrödinger equation for the time independent case choos-
ing the 1D simple harmonic oscillator as an example.
Solution: The time independent Schrödinger equation for a 1D simple har-
monic oscillator is
h2 d2

1 2 2
− 2 + µω x ψ(x) = Eψ(x),
8π µ dx2 2
q
where µ = reduced mass of the system, ω = µk is the angular frequency,
k = force constant and E = energy of the 1D simple harmonic oscillator in
state ψ(x).
4) Of the three functions Ψ1 , Ψ2 and Ψ3 , choose the acceptable wavefunction
citing proper reasons. Normalise the acceptable wavefunction. A1 , A2 and A3
are real constants:
Ψ1 = A1 sinx, [0 ≤ x ≤ 2π]
Ψ2 = A2 sin−1 y, [−1 ≤ y ≤ 1]
Ψ3 = A3 exp(z), [−∞ ≤ z ≤ ∞]
Solution: For Ψ1 , please see question 1 of year 2008.

For Ψ2 , please see question 2 of year 2012.
Ψ3 = A3 exp(z), [−∞ ≤ z ≤ ∞] becomes infinite for z = ∞. Thus it is not
an acceptable wavefunction.
5) From the probability density of 1s electron show that the most probable
137
distance of electron from the nucleus is equal to the Bohr radius. Given
1
Ψ1s = p 3 e−r/a0 ,
πa0
where a0 is the Bohr radius.

6) Find the value of the commutator (x̂p̂x − p̂x x̂) of the quantum mechanical
operators x̂ and p̂x .
7) For the particle in a box, in one dimension, with infinitely high potential at
the walls, write down the expression for energy and wavefunction. Show that
here wavefunction Ψ1 (n = 1) and Ψ2 (n = 2) are orthogonal to each other.
Solution: The expressions for energy and wavefunction of particle in a 1D
box are
r
2 nπx
ψ(x) = sin
L L
2 2
nh
E= , L = Length of the box.
8mL2
(ii)
ZL ZL r r
2 πx 2 2πx
Ψ1 Ψ2 dx = sin sin dx
L L L L
0 0
ZL
1 2πx πx
= 2sin sin dx
L L L
0
ZL
1 πx 3πx
= cos − cos dx
L L L
0

1 L L L L
= sinπ − sin0 − sin3π + sin0
L π 1π 3π 3
= 0.
Thus, the wavefunctions Ψ1 (n = 1) and Ψ2 (n = 2) are orthogonal to each

other.
8) An electron is confined in a 1D box of side 2Å. Calculate the frequency
of the photon which can produce an excitation from n = 1 to n = 2. Given
me = 9.1 × 10−28 g.
Solution: If ν be the frequency of the photon that can produce the excitation
from n = 1 to n = 2 then
4h2 h2 3h2
hν = E2 − E1 = − =
8mL2 8mL2 8mL2
3 × 6.626 × 10−34
ν= −31 −10 2
= 6.826 × 1015 sec−1 .
8 × 9.1 × 10 × (2 × 10 )
9) Show that eikx is an eigenfunction of the operator p̂x . What is the eigen
value?
Solution:
d
p̂x eikx = −i~ eikx = −i~ × ikeikx = k~eikx
dx
138
Thus, eikx is an eigenfunction of p̂x and the eigenvalue is k~.
10) For a particle in a cubical box, write down the energy values for the
condition: nx + ny + nz = 4 and indicate the level of degeneracy, if any.
Solution: nx , ny , nz can have only integer value (6= 0). Thus, nx +ny +nz = 4
will be possible only for (nx = 1, ny = 1, nz = 2), (nx = 1, ny = 2, nz = 1)
and (nx = 2, ny = 1, nz = 1). Thus, the energy value will be equal to
h2
(n2x + n2y + n2z ) 8mL 2 . The level of degeneracy is 3.
11) Write down the Schrödinger equation for H-atom. What is an orbital?
Draw schematically the 2s orbital of H-atom.
Solution: The Schrödinger equation for H-atom
h2
2
∂2 ∂2 e2

∂
− 2 + + − ψ(x, y, z) = Eψ(x, y, z),
8π µ ∂x2 ∂y 2 ∂z 2 4π0 r
where r = nucleus-electron separation distance, µ = reduced mass.

An orbital is a three-dimensional space around the nucleus, where the prob-
ability of finding electron is maximum.
Figure 12: 2s orbital in H-atom
1999: 1) What is the kinetic energy of an electron whose de Broglie wavelength is

10−10 m?
Solution: The momentum of the electron with de Broglie wavelength of
10−10 m is
h 6.626 × 10−34
p= = −10
= 6.626 × 10−24 kg.m.sec−1
λ 10
Therefore, the kinetic energy of the electron will be
p2 (6.626 × 10−24 )2
= −31
= 2.412 × 10−17 J
2m 2 × 9.1 × 10
2) Explain the phenomenon of photoelectric effect in the light of Einstein’s
theory.
Solution: See the relevant section of the text (section ??).
3) Sodium has an ionization energy of 5.12 eV. Calculate the enegy of pho-
toelectrons, when light of wavelength 200 nm shines on it. Work function of
Sodium = 2.3 eV.
Solution: When a metal having work function W0 is irradiated with a light
of wavelength λ, the energy of photoelectrons (E) emitted is
hc
E= − W0
λ
6.626 × 10−34 × 3 × 108
= −9
− 2.3 × 1.602 × 10−19
200 × 10
= 9.939 × 10−19 − 3.6846 × 10−19
= 6.2544 × 10−19 J = 3.9041eV
139

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Mini book: Chapter planning1:

1. Basic concepts in Quantum Chemistry

1.1. Wave-particle duality :

Figure 1: Rope bridge

On the other hand, a particle is considered as a localized thing with

Figure 2: Wave and particle natures

Photo-electric effect was first described successfully by Albert

Thus these two experiments/observations clearly demonstrate

1.1.2. de Broglie hypothesis [1924]

Figure 3: Wave on a circle

If we assume the wave to be a matter wave then we can use

is the corresponding eigenvalue.

Âkf = k Âf, Operator does not operate on a constant.

then the operator Â is called a linear operator.

where ∗ represents complex conjugate. Such operators are also

But, taking transpose followed by complex conjugation is the

Multiplying both sides (from left) by f ∗ and integrating the

Now, taking adjoint of the above equation, we get

Since f ∗ f dτ 6= 0, this means a − a∗ = 0 =⇒ a = a∗ , which

R ∗ f and g are two different functions, b 6= a. This means,

• If a function is square integrable i.e if for a function (f ),

over a space then it will be possible to normalize that function.

• Orthogonality of two functions simply means that the two func-

X The above example reflects a very important characteristic about

[x̂, ŷ] f = x̂ŷf − ŷx̂f = xyf − yxf = 0, x and y are numbers

[x̂, ẑ] = [ŷ, ẑ] = 0 can similarly be proved.

[p̂x , p̂y ] f (x, y) = p̂x p̂y f (x, y) − p̂y p̂x f (x, y)

How did we reach at this equation? Simply by combining all

V̂configuration = V ({xi , yi , zi }) (31)

– Since V̂configuration has no real mathematical operator, it is a

Ĥψ(r) = Eψ(r) (38)

Orthogonality and normalization of wavefunctions:

• As mentioned earlier, orthogonality of wavefunctions represent section

is called the overlap integral and it represents how much alike

Figure 4: Pictorial representation of particle in a 1D box

What real system does a particle in a box model represent?

Since, n is an integer, the result of integration of cos 2nπx

• More fun with particle in a box model

Figure 5: wavefunctions and probability density for particle in a 1D box

within the box. Note, for mth excited state, n = m + 1.

Numerical illustration of quantum weirdness:

∗ The wavefunction of the particle in first excited state is

Similarly, the probability of finding the particle slightly

∗ Thus, we see that there is a finite probability of finding

∗ Let us have a look at the probability density plot

∗ This plot tells us, how probable is it to find the

∗ As the figure suggests, the probability of finding

∗ It seems that the particle is trying to avoid the

∗ This is weird. Classically, the probability of finding

∗ This is another weird nature of quantum particles

OK, we have talked enough about weirdness of a particle in a

Thus, the states of a particle in a 1D box are orthogonal

– Studying physically observable quantity of real systems

8 × 9.1 × 10−31 kg × 3.0 × 108 m.sec−1 2

This wavelength is much larger than the experimental

1.5.2. Free particle

is infinite and hence the free particle wavefunctions are not

“all space” represents the boundary condition for the system.

• So, if we know these four expectation value, we can check if

Thus, the average position of the particle is at the middle of the

• Calculating hpx i for particle in a 1D box:

We see that the expectation value of linear momentum for a

• We have seen that the eigenfunction of T̂x operator (which