Professional Documents
Culture Documents
Block 2
Block 2
QUANTUM MECHANICS-I
Indira Gandhi National
Open University
School of Sciences
Block
2
APPLICATIONS OF QUANTUM MECHANICS
UNIT 5
Simple One-Dimensional Potentials-I 7
UNIT 6
Simple One-Dimensional Potentials-II 47
UNIT 7
Simple Harmonic Oscillator-I 87
UNIT 8
Spherically Symmetric Potentials 119
UNIT 9
The Hydrogen Atom 143
Programme Design Committee
Prof. V.B. Bhatia, Retd. Prof. Enakshi Sharma Prof. G. Pushpa Chakrapani Prof. Suresh Garg, Retd.
University of Delhi, Delhi University of Delhi, South BRAOU School of Sciences,
Campus, Delhi Prof. Y.K. Vijay IGNOU, New Delhi
Prof. Abhai Mansingh, Retd.
University of Delhi, Delhi Prof. H. S. Mani, Retd. University of Rajasthan, Prof. Vijayshri
IIT Kanpur Rajasthan School of Sciences,
Prof. Feroz Ahmed, Retd.
Prof. S. Annapoorni Prof. J. Nag, Retd. IGNOU, New Delhi
University of Delhi, Delhi
University of Delhi, Delhi Jadavpur University Prof. S. R. Jha
Prof Yashwant Singh, Retd.
Prof. D. Choudhury Prof. Zulfequar, School of Sciences,
Banaras Hindu University,
University of Delhi, Delhi Jamia Milia Islamia,New Delhi IGNOU, New Delhi
Varanasi
Prof. T.R. Seshadri Dr. Om Pal Singh Prof. Shubha Gokhale
Prof. Deepak Kumar
University of Delhi, Delhi IGCAR, Kalpakkam, School of Sciences,
J.N.U., New Delhi
Tamil Nadu IGNOU, New Delhi
Prof. Vipin Srivastava Prof. S. Ghosh
J.N.U., New Delhi Prof. Prabhat Munshi Prof. Sanjay Gupta
Central University of
IIT Kanpur School of Sciences,
Hyderabad, Hyderabad Prof. Neeraj Khare IGNOU, New Delhi
Prof. G.S. Singh IIT Delhi, Delhi Prof. R.M. Mehra, Retd.
Dept. of Electronics, South Dr. Subhalakshmi Lamba
IIT Roorkee Prof. V.K. Tripathi
Campus, University of Delhi, School of Sciences,
Prof. A. K. Rastogi. IIT Delhi, Delhi IGNOU, New Delhi
Delhi
J.N.U., New Delhi Prof. Pankaj Sharan, Retd.
Prof. S. K. Kulkarni Dr. M.B. Newmai
Prof. A. K. Ghatak Jamia Milia Islamia, School of Sciences,
New Delhi Pune University/
IIT Delhi, Delhi IGNOU, New Delhi
IISER Pune, Pune
Prof. Rupamajari Ghosh Prof. Kirti Ranjan
J.N.U., New Delhi University of Delhi, Delhi
4
_BLOCK 2 : APPLICATIONS OF QUANTUM MECHANICS
In Block 1 of this course we have introduced you to the basic concepts of quantum
mechanics. Quantum mechanics has forced us to reconsider our deepest convictions about
the reality of nature. For example, the idea that wave-particle duality is an inherent property of
all the elements that make up the physical universe does away with the distinction between
matter and radiation (which is at the root of classical physics). Then you have seen how
classical determinism and causality are called into question by quantum mechanics through
the uncertainty principle and the probabilistic description. These fundamental ideas were built
into a mathematical framework which you studied in Units 3 and 4.
The methods of quantum mechanics become important when we talk of microscopic systems,
far removed from our daily experiences. Yet it affects our lives in many different ways,
because in today’s world, a lot of the technology we take for granted owes its origins to
quantum mechanics: shrinking transistor sizes to power laptops and mobiles, medical
technology like MRI and PET and so on. This has become possible, in part, because of one
important aspect of quantum mechanics: its ability to predict. You will discover its power in
this block when you solve the Schrodinger equation for different potentials. You will learn how
to solve the one-dimensional and the three dimensional Schrödinger equation.
In Unit 5 of this block, entitled “Simple One-Dimensional Potentials-I” you will solve the
one-dimensional Schrödinger equation for the free particle and for a particle confined to a
rigid one-dimensional box. You will study an important distinction between classical and
quantum physics: that when a quantum particle is confined to a tiny region, its energies
cannot be continuous. Rather the particle’s energy can have only specified discrete values,
which depend on the parameters of the system. This idea has important applications in
semiconductor technology and in this context, you will study about the quantum dot. You will
also study the properties of a quantum particle moving in a one-dimensional step potential.
You will learn that it is possible for quantum particles to be found in regions that are
classically forbidden.
In Unit 7 entitled “Simple harmonic Oscillator-I”, you solve the Schrödinger equation for
the one-dimensional harmonic oscillator potential and obtain the eigenfunctions and
the discrete eigenvalues. This is an important problem in physics, because in the
neighbourhood of a local minimum, almost any potential function can be approximated by a
parabola. You will study some examples of simple harmonic oscillator systems like a diatomic
molecule, etc. You will also study a new method of arriving at these results using “ladder
operators” which you learn more about in Unit 12.
The radial part of the three-dimensional Schrödinger equation depends on the potential
function and in Unit 9 we solve the equation for the Hydrogen atom potential, for an electron
moving in the Coulomb field of the proton. We derive the radial wave function and the energy
eigenvalues for the electron. You will learn about the degeneracy of the energy eigen states
and the significance of the quantum number for the hydrogen atom problem.
This Block is mathematically intensive and you should be familiar with the methods of solving
ordinary and partial differential equations, in particular the power series method and special
functions. Please work out all the mathematical steps and solve the SAQs and TQs.
6
Unit 5 Simple One-dimensional Potentials-I
UNIT 5
SIMPLE ONE-DIMENSIONAL
POTENTIALS-I
Structure
5.1 Introduction 5.6 Energy (E) of the Particle is less
Expected Learning Outcomes than V0
5.2 A Free Particle Reflection and Transmission
5.3 Particle in a Box Coefficients
Solving the Schrödinger Equation 5.7 Energy (E) of the Particle is greater
Eigenfunctions and Eigenvalues than V0
The Schrödinger equation
Time Dependent Wave Function Reflection and Transmission
cannot be derived, and like
Probability Density Coefficients the other postulates of
5.4 Quantum Dot 5.8 Summary quantum mechanics, its
5.5 Step Potential and Schrödinger 5.9 Terminal Questions validity lies in its agreement
5.10 Solutions and Answers with experimental results.
Equation
Schrödinger himself applied
his equation to the hydrogen
5.1 INTRODUCTION atom and in fact, it is in the
field of atomic physics that
In Unit 3 of Block 1 you have studied the time independent Schrödinger this equation has been most
equation. In this unit, you will learn how to solve Schrödinger equation in one successful. You should also
dimension. Although the real world is three-dimensional, these one- know that one cannot obtain
dimensional systems are of great interest. This is not only because several an exact solution for neutral
atoms more complex than
physical situations are effectively one-dimensional, but also because a
the hydrogen atom and one
number of more complicated physical problems can be reduced to the solution has to use approximation
of equations similar to the one-dimensional Schrödinger equation. methods, which you study
In Sec. 5.2, you will first study a quantum mechanical free particle, that is one about in Quantum
Mechanics –II in Semester
on which no force is being exerted. This is a particle that cannot be confined
2.
(bound) within a defined region of space by a potential, like a proton in a
nucleus. You will see that a quantum mechanical free particle has a Note also that the
Schrödinger equation is not
continuous spectrum of energy eigenvalues. In Sec. 5.3 we solve the quantum
a relativistic wave equation.
mechanical problem of a particle moving within a limited space like in a rigid So it is used only to study of
box. You will find that the energy eigenvalues of this system are different, a the non-relativistic behaviour
particle in a box has discrete energy levels . In Sec. 5.4 we discuss a quantum of atoms and molecules.
dot which is a practical realization of a particle in a box. A quantum dot is Just like Newton’s second
typically a nano sized semiconductor particle. The optical and electrical law which gives way to the
relativistic force law to study
properties of the quantum dot change with size and material, and they have
relativistic phenomena,
many applications in nano scale devices. there is also a relativistic
wave equation which was
Next in this unit you will learn how to solve the time independent Schrödinger
developed by Dirac in 1928.
equation for a step potential. You will obtain the eigenfunctions and energy
levels for such a potential. You are familiar with steps all around you. So, you
7
Block 2 Applications of Quantum Mechanics
can think of a step as a flat surface, which changes abruptly after a certain
distance so that another flat surface is obtained at a higher level.
Similarly, the step potential changes abruptly, much like a single physical step.
So, a step potential has an abrupt increase or decrease in its value. In
Sec. 5.6, we first define the step potential and write down the time
independent Schrödinger equation for a particle subjected to a step potential.
Then we take up two interesting cases: When the energy of the particle is less
than the height of the step potential (Sec. 5.6.1), and when it is greater
(Sec. 5.7). In both cases, we will get interesting results when we solve the time
independent Schrödinger equation for the step potential.
The step potential can be used to model a variety of physical systems and
some well known applications are seen in semiconductor devices, the physics
of normal-metal superconductor interfaces, and alpha decay in the nucleus.
Solving the step potential problem in this unit will also serve as a good
exercise for you to help you understand the next unit, where you will study
about the barrier potential.
2 d 2 ( x )
V ( x )( x ) E( x ) Hˆ ( x ) E( x ) (5.1a)
2m dx 2
You know that this is the eigenvalue equation for the Hamiltonian operatorc.
Any solution, (x ) , of this equation is the eigenfunction of Ĥ . And the energy,
E, is the eigenvalue of Ĥ corresponding to the eigenfunction (x ) .
( x ) c11( x ) c 2 2 ( x ) c 3 3 ( x ) c n n ( x ) c i i ( x )
i
(5.1b)
And the general time dependent solution is:
iE i t
( x, t ) ci e i (x)
(5.1c)
i
2 ( x )
Note that in Eq. (5.1), the partial derivative has been replaced by
x 2
d 2 ( x )
because (x ) is only a function of x. Now, you know that a free
dx 2
particle is one on which no force is being exerted. You have studied that for a
conservative system, force is related to the potential as follows:
dV ( x )
F(x) (5.2)
dx
So, for a system on which no force is exerted, we will have: The general solution of
dV ( x )
F(x) 0 0 V ( x ) V0 (5.3) d 2 ( x )
dx k 2 ( x ) 0
dx 2
where V0 is a constant potential.
As
Without loss of generality, we can take the constant V0 to be zero. So now we
have a particle of mass m moving freely in space. Putting V ( x ) 0 in Eq. (5.1) ( x ) Ae m1x Be m2 x w
we can write the time independent Schrödinger equation for a free particle here m1 and m2 are the
as follows: solutions of the indicial
equation
2 d 2 ( x )
E( x ) (5.4) m2 k 2 0
2m dx 2
Here
In the classical picture, since the particle is not subjected to any force, its
m1 ik ; m 2 ik
linear momentum p does not change with time. E, the total energy of the
particle (which is equal to its kinetic energy) also does not change with time. E e m1x and e m2 x are the
and p are related by the equation: two linearly independent
solutions.
p2
E (5.5)
2m
From Eq. (1.14) you know that the linear momentum p k . Since we are
considering only one-dimensional motion, we can assume that both the
momentum p and the wave vector k lie along the x-axis. So we write
p p x k . Then the expression for the energy of the particle is:
2k 2
E (5.6)
2m
Let us now solve Eq. (5.1). Rearranging the terms we get:
d 2( x ) 2mE
2 ( x ) (5.7)
dx 2
2mE
Making the substitution k 2 2 we get the following second order ODE:
9
Block 2 Applications of Quantum Mechanics
2
d ( x )
2
k 2( x ) (5.8)
dx
For any given value of E and hence of k, there are two possible solutions to
this equation, which are also linearly independent (read the margin remark):
Thus for one value of E, we have two possible eigenfunctions, 1( x ) and
2(x ) .
Recall from Sec. 8.3.4 that such eigenfunctions which have the same
eigenvalue for a given eigenvalue equation are called degenerate
eigenfunctions (otherwise they are non-degenerate). Thus, 1( x ) and
2 ( x ) are degenerate eigenfunctions. The general solution of Eq. (5.4) is the
linear combination:
( x ) Ae ikx Be ikx (5.10)
The functions sin kx and
You can check for yourself by solving SAQ 1, that (x ) is also an
cos kx , as well as linear
combinations of these 2k 2
eigenfunction of Eq. (5.4) with the same eigenvalue E .
functions are also 2m
solutions of the time
independent Schrödinger SAQ 1
equation for the free
particle. You will see this Show that ( x ) Ae ikx Be ikx is an eigenfunction of the time independent
for yourself when you work Schrödinger equation for the quantum mechanical free particle with an
out SAQ 2.
2k 2
eigenvalue E .
2m
Now, if is positive, you can see that the term e x would increase
exponentially as x . If is negative, the term e x would increase
exponentially as x . So this would not be an acceptable wave function, as
you have studied in Sec. 3.5. You can also check for yourself that 2 ( x )
would also would increase exponentially either as x or as x , if k
had an imaginary part.
So, k should be a real number and therefore k 2 0 . Therefore a quantum
mechanical free particle can have any non negative value of energy:
2k 2
E 0 (5.12)
2m
which is clearly NOT finite. The same is true for 2 ( x ) . So, as you have
studied in Sec. 3.3.3, the eigenfunctions 1( x ) and 2 ( x ) are non-
normalizable.
We can also write down the time dependent wave function for the free particle.
In Sec. 3.4 you have studied that for a stationary state (x ) , the time
dependent wave function has the explicit form (Eq. 3.48):
( x, t ) ( x )e iEt (5.14)
So the time dependent wave function for the free particle with an energy E is
( x, t ) Ae ikx Be ikx e iEt (5.15)
In order to interpret Eq. (5.16) physically, let us consider some special cases.
If we set B = 0, the resulting wave function is the plane wave:
( x, t ) Ae i kx t (5.17)
This function represents a travelling plane wave as shown in Fig. 5.1. This
wave is associated with a free particle of mass m moving along the positive x- Fig. 5.1: A travelling wave.
2k 2
axis with a definite momentum of magnitude ħk and an energy .
2m
The probability density corresponding to the wave function of Eq. (5.17) is:
2
P ( x, t ) * ( x, t )( x, t ) A (5.18)
d d ikx
pˆ x 1 x i 1 x i e i ike ikx ke ikx
dx dx
d d ikx
pˆ x 2 x i 2 x i e
dx dx
The energy E [E(k)] and the momentum p [p(k)] of a quantum mechanical free
particle are both constants of motion and are defined in terms of k. k also
characterises the eigenfunction (x ) for the quantum mechanical free particle
and hence we call k a quantum number.
You may now like to answer an SAQ.
SAQ 2
Show that (i) ( x ) sin kx and (ii) ( x ) cos kx are solutions of the
Schrödinger equation for the free particle (Eq. 5.7).
0 for 0 x L
V (x) (5.19)
x 0 and x L
V=0
The “particle in a box” problem is also called the “infinite potential well” or the
“infinite square well potential” problem. A simple classical analogue of this
system could be a ball bouncing elastically between two rigid walls (Fig. 5.3). x=0 x=L
Inside the box, the particle is “free” because the potential, and hence, the Fig. 5.2: Potential
force on the particle is zero. As the particle bounces back and forth, its speed function for a one-
dimensional box.
and kinetic energy remain constant. In the classical picture, the particle could
have any speed inside the box, and any kinetic energy. Let us now solve the
Schrödinger equation for this potential and determine the eigenfunctions and
eigenvalues of the Hamiltonian operator for this system.
5.3.1 Solving the Schrödinger Equation
v
For the (free) particle inside the box, V 0. The Schrödinger equation for the
stationary state wave function (x ) is:
2 d 2( x ) v
E( x ) for 0 x L (5.20)
2m dx 2
Since the walls of the box cannot be penetrated, the particle cannot be found x
beyond the walls (that is in the regions x 0 and x L ). So, the quantum Fig. 5.3: A ball going
mechanical probability of finding the particle in the region beyond the box, back and forth between
should be zero. Therefore ( x ) 0 for x 0 and x L . Further, the wave rigid walls.
functions for a physical system are always single-valued and continuous. To
satisfy this condition, (x ) should also be zero at the boundaries of the box,
i.e. at x 0 and x L . So, we can write the boundary conditions for the
wave function (x ) as:
( x 0 ) ( x L ) 0 (5.21)
13
Block 2 Applications of Quantum Mechanics
2mE
With these boundary conditions, we now solve Eq. (5.20). We put k 2 in
2
Eq. (5.20) and get the following second order ODE:
d 2( x )
k 2 ( x ) 0 (5.22)
dx 2
You have solved this equation in Sec. 5.2 (Eq. 5.8). From SAQ 2 you know
that ( x ) sin kx and ( x ) cos kx are both solutions of this equation. So we
In general, for can write the general solution for Eq. (5.22) as:
sin x 0 x n ( x ) A sin kx B cos kx (5.23)
where
To represent the particle in the box, this wave function must satisfy the
n 0,1,2,3...
boundary conditions given in Eq. (5.21). So, we now impose these conditions
However the wave on the wave function (x ) of Eq. (5.23).
function for a negative
value of n is not linearly ( x 0 ) 0 A sin k (0 ) B cos k (0 ) 0 or B 0 (5.24)
independent of the wave With B 0 , the expression for the wave function of Eq. (5.23) becomes
function for the positive
value of n. For example ( x ) A sin kx (5.25)
for n = 1: Applying the boundary condition on the wave function at x L , we get:
1 ( x ) A sin
x
( x L ) 0 A sin k (L ) 0 (5.26)
L
And for n=1 Clearly, A 0 , because if it were, the wave function (x ) would be zero at all
x 2
1 ( x ) A sin values of x and the probability density ( P ( x, t ) ( x ) ) for finding the particle
L
So, at any position x would also be zero. This is an unphysical solution and
1( x ) 1( x ) cannot be considered. In Eq. (5.26), since A 0 , we must have (read the
So we can consider only
margin remark):
one of these solutions, sin k (L ) 0 kL n , n 0,1,2,3.... (5.27)
either n=1 or n=1. And
For n 0 , k would be equal to zero and hence, (x ) would be zero at all
so on for all values of n.
values of x, once again an unphysical solution. So we discard the value
of n 0 in Eq. (5.27) and write the possible values of k, which satisfy the
boundary conditions as:
n
k , with n 1,2,3.... (5.28)
L
Notice from Eq. (5.28) that the all values of k are not permitted. k can have
only the following discrete or “quantized” values:
2 3
k , , ........
L L L
Therefore, we write k with a subscript n to denote the value of n:
n
kn , with n 1,2,3.... (5.29)
L
We can now write down the possible stationary state solutions for this system
(which are the eigenfunctions) and determine the corresponding energy
eigenvalues.
5.3.2 Eigenfunctions and Eigenvalues
On substituting the value of k n in Eq. (5.25) we can write the stationary state
14 wave function as:
Unit 5 Simple One-dimensional Potentials-I
nx
n ( x ) A sin k n x A sin , 0 x L and n 1,2,3....
L
(5.30)
n
The subscript n once again indicates the value of k k n in the wave
L
function. As you can see, for each value of n we get a different wave function.
Each of these functions 1( x ), 2 ( x ),... is an eigenfunction of the Hamiltonian
operator for the particle in a box. What are the corresponding eigen energies
En?
We determine the energy eigenvalues En from the Schrödinger equation for
the eigenfunction n (x ) :
2 d 2 n ( x )
En n ( x ) (5.31) Fig. 5.4: The energy levels
2m dx 2
for a particle in a one-
nx dimensional box. The
Since n ( x ) A sin , we get ground state energy is E1.
L
d n ( x ) n nx
A cos
dx L L
and
2 2
d 2 n ( x ) n nx n
A sin n (x )
dx 2 L L L
2 n
2
n 2 2 2 In general, if we have a
n ( x ) E n n ( x ) E n (5.32)
2m L 2mL2 bounded system, or in
the terms of classical
So the energy eigenvalues for the quantum mechanical particle in the box mechanics, if the motion
are: is confined to a finite
region of space, solving
2k n 2 n 2 2 2 the corresponding
En with n 1,2,3.... (5.33)
2mL2 2mL2 Schrödinger equation
will give us a discrete
As you can see, the particle can have only certain discrete values of energy. energy spectrum.
The energy spectrum is no longer continuous.
From Eq. (5.33) we can write for n = 1:
2k n 2 2 2
E1 (5.34)
2mL2 2mL2
And therefore
En n 2E1 (5.35)
It is important to note the following properties of the energy eigenvalues of a
particle in a box:
1. Now that the particle has been confined to a box, you no longer have a
continuous energy spectrum. Its energy can take only the discrete values
given by Eq. (5.33) and shown in Fig. 5.4. This is in contrast to the
15
Block 2 Applications of Quantum Mechanics
classical picture in which all finite values of the energy ( E 0 ) are
allowed.
2. The quantization of energy follows from the boundary conditions imposed
on the wave function due to the confinement of the particle.
3. The minimum energy of the particle in the box is not zero but has a finite
2 2
value: E1 . So in the quantum mechanical system, the particle
2mL2
can never be at rest. This is in keeping with the uncertainty principle and
the concept of zero point energy that you have studied in Unit 2. E1 is the
zero point energy for this system.
Notice that the wave function defined by Eq. (5.30) is not normalized. Let us
now determine the normalization constant A in the following example.
Example 5.2
Determine the normalization constant A for the following eigenfunction of a
particle confined in a box of length L:
nx
L
n ( x ) A sin k n x A sin , 0xL
nx dx L
sin2
0 L
Solution : We use the normalization condition given by Eq. (3.50) with
1 L 2nx
1 cos dx nx
2 0 L n * ( x ) A * sin . We can write the normalization condition as:
L
L
1 L 2nx L L
x sin nx nx 2 2 nx
2 2n L 0 A * sin
L
A sin
L
dx 1 A sin
L
dx 1
0 0
L
On evaluating the integral we get (see the margin remark):
2
L 2
A 2 1 A
2 L
Substituting the value of A from Example 5.2 into Eq. (5.30), we can write the
eigenfunction n (x ) for a particle confined in a line segment of length L as:
2 nx
n (x) sin with n 1,2,3.... (5.36)
L L
The corresponding energy eigenvalues are given by Eq. (5.33). Let us write
down the eigenfunctions and energy eigenvalues for the first three states of
the system (n = 1, 2 and 3 respectively):
2 x 2 2
1( x ) sin ; E1 (5.37a)
L L 2mL2
2 2x 2 2 2
2( x ) sin ; E2 4E1 (5.37b)
L L mL2
2 3x 9 2 2
3 ( x ) sin ; E3 9E1 (5.37c)
L L 2mL2
These eigenfunctions are shown in Fig. 5.5.
16
Unit 5 Simple One-dimensional Potentials-I
3(x)
2(x)
1(x)
x
x=0 x=L
You can see that each of the eigenfunctions has a node (a point where the
wave function goes to zero) at x 0 and x L. The number of nodes in the
eigenfunction increases with the value of n. The eigenfunctions corresponding
to different eigenvalues are orthogonal, as you can check for yourself in the
next SAQ.
SAQ 3
Show that the eigenfunctions for the particle in a box are orthogonal.
E1 2.5 2 2 2.5 ( ) 2 1.054 10 34
2
J 2.7 10 67 J
The kinetic energy of the car is
1 1
K mv 2 0.2 kg 0.1ms 1 1.0 10 3 J
2 2
2
(ii)
We calculate the value of n for which the energy of the bound state would be
equal to the kinetic energy of the car. So using :
K E n 1.0 10 3 J n 2 E1 and substituting for E1 we get:
17
Block 2 Applications of Quantum Mechanics
3
1.0 10 J
n2 n 6 1031
67
2.7 10 J
So the minimum energy of the car is too small to be measured, and we can
take it to be zero. Also the energy of the classical particle is characterized by
an extremely large quantum number. As you have studied in Sec. (4.6.3), the
Correspondence principle tells us that we need not use the quantum
formalism for such large quantum numbers. We can use Newtonian
mechanics. If n is small, on the other hand, we cannot use classical
mechanics.
Unlike for the free The integer n that is used to index the eigenfunctions n (x ) and the energy
particle, for the particle eigenvalues E n is called the “energy quantum number” or the “principle
in a box, the
eigenfunctions of the
quantum number”. As you can see in Fig. 5.4, corresponding to any allowed
Hamiltonian operator are
value of n you have a discrete eigen energy (level). The state 1( x ) is the
not the simultaneous ground state eigenfunction and E1 , the ground state energy. The state
eigenfunctions of the 2 ( x ) is the first excited state and E 2 , the energy of the first excited state.
momentum operator, The state 3 ( x ) is the second excited state and E 3 , the energy of the second
which is why we call n
the energy quantum
excited state. You can think that these energy states are like the energy
number. You will see this levels in an atom. Suppose a particle “occupies” the energy state (or energy
for yourself in Terminal level) E1 . On being given an energy ( E 2 E1 ), it can move into the first
Question 8. excited state E 2 . On the other hand, if the particle occupies the first excited
state E 2 , it can emit an energy ( E 2 E1 ) and move to the ground state E1 .
Note from Eq. (5.33) that the eigen energy values depend upon the size of
the box, L and the mass of the particle m. The energy difference between the
corresponding energy levels also depends on L and m. The energy difference
between the nth and (n+1)th energy levels is:
2 2 2 2
E E n 1 E n (n 1) 2 n 2 ( 2n 1) (5.38)
2mL2 2mL2
What does Eq. (5.38) tell us? Smaller the region in which a particle is
confined (L), the larger is the difference in energy (E) between the
consecutive energy levels. Conversely, as L increases, the energy separation
decreases. When L is much larger than atomic dimensions, the energy
separation is so small that we approach the classical correspondence limit.
Note that for large L, the zero point energy also tends towards zero, as you
have seen in Example 5.3.
In fact in the limit when mL2 becomes much larger than h2 ( mL2 2 ), which
is typically true for everyday macroscopic objects, the spacing between the
energy levels keeps getting smaller. So the energy of a classical particle in a
box will vary continuously and quantum effects will not be visible.
Let us now try to model the electron in an atom like a particle in a box.
Example 5.4
Calculate the energy levels of an electron confined to an atomic box of size
1.0 Å.
Solution : The energy levels for the electron are calculated using Eq. (5.33)
18 with L 1.0 Å 1.0 10 10 m . Now,
Unit 5 Simple One-dimensional Potentials-I
n 2 2 2 n 2h 2
En , n = 1, 2, 3,…
2 me L2 8m e L2
For n = 1:
E1
12 h 2
h2
6.626 10 34 Js 2
0.602 10 17 J 38 eV
So the remaining energy levels are:
E n n 2 E1 38n 2 eV
2 nx
Pn ( x, t ) Pn ( x ) n ( x ) 2 sin2 (5.42)
L L
From Eq. (5.42), you can see that Pn (x ) depends on the position of the
particle in the box. In Fig. 5.6 below, we have plotted the values of Pn (x )
corresponding to first three eigenfunctions of the system (for n = 1, 2, 3).
The probability of finding the particle is maximum around the maxima (humps)
of the probability distribution and is zero at the nodes. So the probability of
finding the particle in any finite region of the box also changes with the
eigenfunction.
19
Block 2 Applications of Quantum Mechanics
P3 ( x )
P2 ( x )
P1( x )
x
x=0 x=L
2
Fig. 5.6: The probability density ( n (x ) ) as a function of position for the first
three eigenfunctions of a particle in a box.
3L / 4
1 L 2x
x sin
L 2 L L / 4
1 3L L L 2 3L L 2 L
sin sin
L 4 4 2 L 4 2 L 4
1 L L 3 L L 1 2 1 1
sin sin
L 2 2 2 2 2 L 2 2 2
2 x
ii) For x * x sin , x1 0 and x 2 L 4 the probability is:
L L
L/4 2 L/4
2 x 1 L 2x
P
L
sin
L
dx x
L 2
sin
L 0
0
20
Unit 5 Simple One-dimensional Potentials-I
1 L L 2 L 1 L L 1 1
sin
L 4 2 L 4 L 4 2
4 2
You may now like to work out an SAQ on calculating the probability.
SAQ 4
Let us compare this with the classical picture. Classically, the particle bounces
back and forth between the walls. Since the kinetic energy of the particle is
constant, it moves at a constant speed between collisions with the walls.
Therefore, it spends the same amount of time in all intervals which have an
equal length. So the normalized probability per unit distance, of the particle
being found anywhere in the box is just 1/L which is independent of the
position of the particle. This is clearly not the case for the quantum mechanical
particle. However, when n is very large the wave function begins to have so
many nodes and humps that in the limit as n each position of the particle
is equally probable. Then the quantum mechanical probability distribution
begins to look like the classical distribution.
For a large value of n, you would observe only the average value of the
probability density which is
2 nx 2 1 1
Pn ( x, t ) sin2 (5.43)
L L L 2 L
(This is because the average of the square of the sine function over one or
more cycles is always half.)
Our understanding of the way charge carriers behave in materials is also an
application of quantum mechanics. Solving the Schrödinger equation using the
exact potentials experienced by the charge carriers is very complicated.
However, it is often possible to understand the observed phenomena using
simple models of the potential which are easier to solve.
Some of you may have read (or you can read now) popular science articles
about “nano” sized materials like quantum wells, quantum wires and quantum
dots and how they have exciting applications, mainly because they exhibit
quantum effects. In the next section we study about quantum dots. We can
understand the special properties of a quantum dot by modelling a charge
carrier inside the quantum dot as a particle in a box.
(a) (b)
Fig. 5.7: Energy levels of a) a bulk semiconductor; and b) a quantum dot of the
same semiconductor.
Notice that for the
electron in the Absorption and emission of light by these quantum dots (as in any atom or
semiconductor quantum molecule) takes place by the transition of charge carriers between these
dot we are writing the energy levels.
mass of the electron as
m e * and not me. This is Suppose an electron occupying the energy state j in a quantum dot of size D
because in a
makes a transition to state i. Let us assume that the quantum dot is a one-
semiconductor, the
electron has an effective dimensional rigid box of size D (read the margin remark). Using Eq. (5.33) for
mass m e * (which is the energy of the electron, we can write the expression for the energy emitted
much less than the free in this transition as:
electron mass m e ) which
decides to a large extent j 2 22 i 2 2 2
how the electron
E ji E j E i
2me D 2 2m e D 2
behaves inside a
semiconductor! It is
because of this that the 22
( j2 i2) (5.44)
de Broglie wavelength in 2me * D 2
a semiconductor is
typically of the order of This energy difference depends on the size of the dot D. If D increases, other
nanometers, and not
parameters remaining the same, the value of E ji decreases. This is depicted
angstroms as for a
in Fig. 5.8 below.
conduction electron in a
metal.
22
Unit 5 Simple One-dimensional Potentials-I
Eji
j
i Eji
i
L1 L2
(a) (b)
Fig. 5.8: Energy level variation with size. For a box of size a) L1; and b) L 2 with
L1 L2 , the difference between the energy levels E ji E ji .
This energy difference is emitted from the dot as a photon of light. What is the
wavelength of this photon? If the frequency of the emitted photon is and its
wavelength ( c ), then:
hc 2 2
E ji h ( j2 i2)
(5.45)
2me D 2
So the wavelength of the emitted photon is directly proportional to the size of
the dot D. As the size of the dot increases, the wavelength of the emitted
photon also increases. As D increases, even though the material of the dot
may remain the same, the wavelength of the emitted lights changes from the
blue towards the red end of the visible spectrum! So by tuning the size of the
quantum dot in the process of preparation, you can obtain a specific
wavelength of the emitted light.
Several other applications of the quantum dot are also related to the fact that
its energy levels can be tuned by its size. Quantum dots are used in single-
electron transistors, solar cells, LEDs, lasers, single-photon sources, cell
biology research, microscopy, and medical imaging.
0, for x 0
V (x) (5.46)
V0 0, for x 0
V(x)
V V0
I II
V 0
0 x
Fig. 5.9: A step potential. Note that the potential is zero in Region I and it has a
non-zero value (V0 ) in Region II.
In Fig. 5.9, note that the step potential V (x ) is zero in the region x 0 and
non-zero (equal to V0 ) in the region x 0. Note also from Fig. 5.10 that the
step potential is discontinuous at x 0.
You may like to ask: What does such a potential mean physically? To
understand this, and to get a physical picture of the potential, let us see what
happens to a particle subjected to the step potential.
Let us consider a particle of mass m having kinetic energy, E, and moving
from left to right along the x-axis as shown in Fig. 5.10.
(a) (b)
Fig. 5.10: Classical picture of a particle with energy (a) lower than the step
potential V0 and (b) higher than the step potential V0 .
Let us first ask: What would happen if the particle was a classical particle?
From classical mechanics, you know that if the energy (E) of the particle were
24 less than the step potential V0 , that is, if E < V0 , then the particle would not be
Unit 5 Simple One-dimensional Potentials-I
able to enter Region II from Region I (see Fig. 5.10a). A classical particle for
which E < V0 , would be reflected at the step. However, if the energy of the
classical particle was greater than V0 , it would be able to cross the step
potential and move into Region II (see Fig.5.10b).
Let us now ask: What would happen to a quantum particle subjected to this
potential? Refer to Fig. 5.11. Note that the particle is incident from Region I of
the step potential (V0 ). Note that in the Region I, the energy (E) of the particle
is purely kinetic energy, while in Region II, the energy is partly kinetic and
partly potential. Now recall from Unit 3, how quantum mechanics differs
fundamentally from classical physics. According to quantum mechanics, the
wave function of the particle has finite value in Region II, which means that
there is a finite probability of finding the particle in Region II even when the
particle has less energy than the potential! This is the result we get when we
solve the Schrödinger equation.
V (x )
V V0
I II
(a)
E V 0
0 x
V (x )
V V0
I II (b)
E
V 0
0 x
Fig. 5.11: A particle with energy E is incident from Region I and subjected to a
step potential V0 at x 0. We consider two cases, a) when E < V0 ;
b) when E > V0 .
2 d 21
E 1 x 0 (5.47a)
2m dx 2
2 d 2 2
V0 2 E 2 x 0 (5.47b)
2m dx 2
25
Block 2 Applications of Quantum Mechanics
We solve the Schrödinger equation for the two regions [Eqs. (5.47a and b)].
We also have to apply the boundary conditions to get acceptable wave
functions. Note that we have denoted the solutions of the Schrödinger
equation in Regions I and II as 1 and 2 in Eqs. (5.47a and b). The
boundary conditions for this problem are: At x 0
1 ( x 0) 2 ( x 0) (5.48a)
d1 d
and 2 (5.48b)
dx x 0 dx x 0
Now, there are two interesting possibilities regarding the energy of the particle
with respect to the step potential. The first case is when the energy of the
particles is less than the step potential V0 and the second, when it is greater.
Therefore, in Secs. 5.6 and 5.7, we will solve Eqs. (5.47a and b) for the
following two cases:
Case 1: The energy E of the particle is less that V0 (Fig. 5.11a)
Case 2: The energy E of the particle is greater than V0 (Fig. 5.11b)
Let 1( x ) be the solution of the Schrödinger equation for the particle in
Region I. Since the potential is zero in this region, the particle is free and the
corresponding time independent Schrödinger equation is:
2 d 21
E1 (5.49a)
2m dx 2
d 21 2mE
1 0 (5.49b)
dx 2 2
d 21
k121 0 (5.49c)
2
dx
2mE
where k1 (5.49d)
2
You know [Eq. (5.10)], that the solution of Eq. (5.49c) is:
You know that, the term A e ik1x in Eq. (5.50) represents a wave of amplitude
A travelling in the positive x-direction while the term B e ik1x represents a
26
Unit 5 Simple One-dimensional Potentials-I
wave with amplitude B travelling in the negative x-direction. The second term
in Eq. (5.50) is a wave reflected at the step potential (see Fig. 5.12).
Ae ik1x Be ik1x
I Ce x II V V0
E
V 0
0
x
Fig. 5.12: The solutions [Eqs. (5.47a and b)] of the Schrödinger equation for a
free particle in Regions I and II of the step potential.
2 d 2 2
V0 2 E 2 (5.51a)
2m dx 2
d 2 2 2m
(V0 E ) 2 0 (5.51b)
2
dx 2
2m(V0 E )
We put (5.51c)
2
d 2 2
2 2 0 (5.51d)
dx 2
2 ( x ) Ce x (5.52)
Can you say: Why have we not included the term Dex in Eq. (5.52)? Recall
what you have learnt in Unit 3 about physically acceptable wave functions.
27
Block 2 Applications of Quantum Mechanics
x
You know that it is because the term De represents an exponentially
increasing wave function in the Region II. It is not physically meaningful since
an acceptable wave function must remain finite as x . Thus, we must have
D 0.
Let us now put the solutions of the time independent Schrödinger equation for
the step potential defined by Eqs. (5.49c and Eq. 5.51d), at one place. The
solutions are:
Remember that A and B are the amplitudes of the incident wave and the
reflected wave in Region I and C represents the amplitude of a wave that
decreases exponentially in Region II. Applying the second boundary condition
[Eq. (5.48b)], we get:
d1 d 2
dx dx
Let us now solve Eqs. (5.53a and b) to determine the constants A, B and C.
Adding Eqs. (5.53a and b), we get:
i
2 A 1 C
k1
2k 1
C A (5.54a)
k1 i
i 2 k1
2B 1 C C B (5.54b)
k1 k 1 i
k i
B 1 A (5.54c)
k1 i
P ( x ) ( x ) ( x ) (5.55)
Note that from Eq. (5.50) that the wave function for the incident wave is
1 ( x ) A e ik1x . Therefore, the incident probability density is given as:
2
P1 ( x ) 1 ( x ) 1 ( x ) ( Ae ik1x )( Ae ik1x ) A
We would now like you to calculate the reflected and transmitted probability
densities corresponding to the reflected and transmitted wave functions using
Eqs. (5.50 and 5.52). Try SAQ 5.
SAQ 5
Determine the reflected and the transmitted probability densities for a step
potential.
Recall Eq. (3.31a) of Sec. 3.3.2 from which the probability current density is
given by:
d d
J
2mi dx dx
i d d
J (5.56)
2m dx dx
Substituting 1 ( x ) and 2 ( x ) in the Regions I and II, respectively, we obtain
the reflected and transmitted probability current densities, respectively. Let
Jr be the probability current density of the reflected wave. Let us take up an
example to calculate it.
Example 5.6
What is the probability current density ( J r ) of the reflected wave?
Jr
i
B B(ik1 ) B B(ik1 ) k1 B B
2m m
29
Block 2 Applications of Quantum Mechanics
k k
Hence, J r 1 B B 1 B 2
m m
You can now calculate the incident probability current density corresponding
to the incident wave function using Eqs. (5.50 and 5.46). Try SAQ 6.
SAQ 6
The transmission coefficient (T) is the probability that the incident particle is
transmitted and is defined as the ratio of the magnitudes of the probability
current densities of the transmitted wave and the incident wave:
Jt
T (5.58)
Ji
Using Eq. (5.57), we can determine the reflection coefficient for a step
potential for E V0 :
2
B
R (5.59)
2
A
k i k 1 i 2
From Eq. (5.54c), we can see that B 2 1 A which means
k 1 i k 1 i
2 2
that B A . Substituting this result in Eq. (5.59), we get R 1.
2. In the Region II, the wave function is non-zero. Therefore, there is a finite
probability ( 2 ( x ) 2 ( x ) C *Ce 2 x ) of finding the particle in Region II;
d 2 2 2m
(E V0 ) 2 0
2
dx 2
31
Block 2 Applications of Quantum Mechanics
2
d 2
k 2 2 0 (5.60)
dx 2
2m(E V0 )
where k 2
2
2 ( x ) F e ik 2 x (5.61)
Ae ik1x V (x ) F eik2 x
B e ik1x
K E V0
E K V 0 V0
0 x
Fig. 5.13: The solutions of Schrödinger equation given by Eqs. (5.50 and 5.61).
The solution of Eq. (5.60) exhibits an oscillatory nature of the wave function
(Fig. 5.13). The general solution of Eq.(5.60) is 2 ( x ) F e ik 2 x G e ik 2 x . The
term F e ik2 x represents a wave travelling along the positive x-axis in the
Region II, while a term like G e ik 2 x would mean a wave travelling along the
negative x-axis in Region II. However, since the particle is incident only from
the left we can assume that G 0.
Let us now apply the first boundary condition: At x 0, [Eq. (5.48a)], we have
1( x ) 2 ( x ). Hence, from Eqs. (5.50 and 5.61), we get:
AB F (5.62a)
Here, F represents the amplitude of the wave in Region II. Similarly, applying
the second boundary condition [Eq. (5.48b)], we get:
d 1 d 2
dx dx
Aik1 Bik1 iFk2
k
AB 2 F (5.62b)
k1
32
Unit 5 Simple One-dimensional Potentials-I
k k 2k1
2 A 1 2 F F A (5.63)
k1 k1 k 2
B 2 k1 k 2 2 d *
R
Jr
(5.65)
d
F * e ik x
2
dx dx
Ji A 2 k1 k 2
ik 2 e ik2 x F *
Similarly, we determine the transmission coefficient (T) using Eq. (5.58) (read
Substituting in
the margin remark): Eq. (5.46) we get the
k 2 2 probability current
Jt F density of the
T m (5.66a) transmitted wave as:
Ji k1 2
A
m i
Jt ik 2 FF *
2m
Substituting Eq. (5.58) in Eq. (5.66a), we get:
2 ik 2 FF *
k 2k1 4k1k 2
T 2 (5.66b)
k1 k1 k 2 k1 k 2 2
You may like to attempt an SAQ on reflection and transmission coefficients.
SAQ 7
Let us now write the wave function for Region I in terms of the incident
amplitude (A).
Substituting Eq. (5.64) in Eq. (5.50), we get the wave function for Region I
when E V0 as:
k k 2 ik1x
1( x ) A e ik1x 1 e for x < 0 (5.67)
k1 k 2
Attempt SAQ 8 to write the wave function for Region II.
SAQ 8
Write the wave function for Region II in terms of the incident amplitude when
E V0 .
Now we will summarize the concepts you have studied in this Unit.
5.8 SUMMARY
The time independent Schrödinger equation for a quantum mechanical
free particle of mass m is:
2 d 2( x )
E( x )
2m dx 2
The general solution of Eq. (5.4) is:
2mE
( x ) Ae ikx Be ikx ; with k 2
2
The quantum number k is real and the free particle can have any non-
negative value of energy:
2k 2
E 0
2m
The energy of the particle does not change with time.
The time dependent wave function for the free particle with an energy
E is:
( x, t ) Ae i kx t Be i kx t
34
Unit 5 Simple One-dimensional Potentials-I
A particle is confined within a length segment lying between x = 0 and
x = L by the following potential function(infinite potential well)
0 for 0 x L
V (x)
x 0 and x L
2 nx iE nt
n ( x, t ) sin e
L L
The eigenfunctions of the system are orthogonal.
Quantum dots (sometimes called artificial atoms) are typically
semiconductor (or metal) particles with sizes ranging from 1 to 100 nm
with properties that are vastly different from the bulk material of which
they are made and depend on the size of the particle.
A change in the size of the dot changes the spacing between the
energy levels. This changes the energy released in the transition of the
electron between the energy levels. So the wavelength of the light
emitted by the quantum dot changes with the size of the dot.
2 d 21
E 1 x 0
2m dx 2
2 d 2 2
V0 2 E 2 x 0
2m dx 2
d 1 d 2
1 ( x ) 2 ( x ) and
dx dx
The Schrödinger equation is solved for two cases: 1) When the energy,
E, of the particle is less than V0 ; 2) when the energy, E, of the particle
is greater than V0 .
2 ( x ) Ce x for 0 x
2mE 2m(V0 E )
where k1 2
and
2
k i 2k1
and B 1 A, C A
k1 i k1 i
and 2 ( x ) F e ik 2 x for 0 x
2m(E V0 )
where k2 ,
2
k k 2k1
and B 1 2 A, F A
k1 k2 k1 k 2
2
k k 4k1k2
R 1 2 and T
k1 k2 k1 k2 2
such that R T 1. A particle with energy higher than the height of
the step potential can get reflected back at the point of discontinuity.
2. Determine the eigenvalues of the operator Hˆ i for the free particle
t
wave function ( x, t ) Ae i kx t .
3x 3x
( x ) A cos B sin
2a 2a
Obtain the values of A and B and the eigen energy corresponding to the
above eigenfunction.
2 nx
9. For the stationary state n ( x ) sin show that
L L
i) pˆ x 0
n 2 2 2
ii) pˆ x 2
L2
12. A beam of particles with energy 7eV is sent towards a step potential of
height 5eV. What fraction of the beam is reflected back?
14. A beam of free electrons are moving from left to right and suddenly
encounters a step potential of height 8 eV. What should be the
approximate energy (E) of the electrons such that 20% get reflected?
Self-Assessment Questions
d 2
1. We use Eq. (5.4) with Ae ikx Be ikx . We first evaluate :
dx 2
d d
Ae ikx Be ikx ik Ae ikx Be ikx
dx dx
d 2 d
ik Ae ikx Be ikx ik 2 Ae ikx Be ikx k 2 ( x )
dx 2 dx
d 2
Substituting k 2( x ) in Eq. (5.4) we get,
2
dx
2 d 2 2k 2 2k 2
x E x E
2m dx 2m 2m
2 d 2 2 2
sin kx E sin kx with E k (i)
2m dx 2m
We have
d2
2
sin kx d d sin kx k d cos kx k 2 sin kx (ii)
dx dx dx dx
d2
Substituting for sin kx from Eq. (ii) into the LHS of Eq. (i) we see
dx
that:
2k 2 2 2
2 sin kx E k
k 2 sin kx
2m 2m 2m
2 d 2 2 2
cos kx E cos kx where E k (iii)
2m dx 2m
d2
Since cos kx k 2 cos kx , we get:
dx 2
2k 2 2 2
2 cos kx E k
. k 2 cos kx
2m 2m 2m
L
n x m ( x ) dx 0 when m n
0
L
2 nx 2 mx
sin sin dx
L L L L
0
2 sin A sin B
L cos( A B ) cos( A B )
2 nx mx dx
sin
sin
L L L
0
1
L
n m x cos n m x dx (see the margin remark)
L
cos
L L
0
L
1 L
sin
n m x L sin n m x
L n m L n m L 0
39
Block 2 Applications of Quantum Mechanics
0 (because m and n are integers
sinn m sinn m 0 )
4. To calculate the probability for the first excited state we use Eq. (5.42) with
2 2x
x * ( x ) sin , x1 L 4 and x2 3L 4 . So the probability is:
L L
3L / 4 2
2 2x 1 3L / 4 4x
P
L sin L dx L 1 cos L dx
L/4
L/4
1 3L L L 4 3L L 4 L
sin sin
L 4 4 4 L 4 4 L 4
1 L L L 1
sin 3 sin
L 2 4 4 2
5. The reflected (Pr) and the transmitted (Pt) probability density is given as:
2 2 2 2
Pr ( x ) Be ik1x B and Pt ( x ) Cex C e 2x
6. The probability current density of the incident wave can be obtain from
Eq. (5.56):
i * d d *
J
2m dx dx
Ji
i
Ae ik1x
d Ae ik1x
Ae ik1x
d Ae ik1x
2m dx dx
Ji
i
2m
k k
A Aik1 A A( ik1) 1 A A 1 A
m m
2
8. Substituting Eq. (5.63 in Eq. (5.61), the wave function for Region II for
E V0 :
2k1 ik 2 x
2 ( x ) A e for x > 0
k1 k 2
40
Unit 5 Simple One-dimensional Potentials-I
Terminal Questions
1. Using Eq. (5.3) we can write
2. The eigenvalue of Hˆ i is determined using Eq. (4.35). With Dˆ Hˆ
t
we can write:
Ĥ E (i)
i Ae i kx t i i Ae i kx t (ii)
t
E (iii)
So the eigenvalue of Ĥ is .
3. The ground state energy of the proton in the nucleus is calculated with
n = 1, mass of the proton is m p 1.673 10 27 kg and L 2.0 10 14 m :
E1
h2
6.626 10 34 Js 2
3 2 2 3h 2
Emin (i)
2me L2 8me L2
41
Block 2 Applications of Quantum Mechanics
hc
Using E in Eq. (i) we get
hc 3h 2 3 h
or L2 (ii)
2
8me L 8mec
3 6.626 10 34 Js 4.0 10 7 m 1/ 2
L
8 9.109 10 31 kg 3.0 10 8 m s 1
0.60 10 9 m 0.60 nm .
1
A a 1 A
2
a
Since V(x) is zero inside the well, the Schrödinger equation is:
2 d 2 ( x )
E ( x ) (i)
2m dx 2
3x
With ( x ) A cos we get:
2a
2 d 2 3x 2 d 3 3x
A cos A sin
2
2m dx 2a 2m dx 2a 2a
2
2 3 2 2
3x 2 3 3x
A
cos A cos
2m 2a 2a 2 m
2a 2a
42
Unit 5 Simple One-dimensional Potentials-I
9 2 2
( x )
8ma 2
9 2 2
E
8ma 2
E 2 10 eV 2 2 E1 E1 2.5 eV
E3 3 3 E1 9 2.5 eV 22.5 eV
* pˆ x2 dx
pˆ x2 (i)
* dx
d d 2
` pˆ x i pˆ x2 2 (ii)
dx dx 2
And
d 2 d d
Ae i kx t
d
ik Ae i kx t k 2 Ae i kx t
dx 2 dx dx dx
p x2
pˆ x n x n x (i)
43
Block 2 Applications of Quantum Mechanics
2 nx
Using n ( x ) sin in Eq. (i), we get :
L L
d d 2 nx
pˆ x n x i n x i sin
dx dx L L
2 n nx 2 nx
i cos in 3 cos (ii)
L L L L L
L
2 nx 2 nx
i) px
L
sin pˆ x
L L
sin
L
dx
0
2 nx
pˆ x n x in cos
3 L
L
L L
2in nx nx in 2nx
px
L 2
sin
L
cos
L
dx
L2
sin
L
dx
0 0
i n L 2nx L i
cos cos 2n cos 0 0
L2 2n L 0 2L
px 0
L
ii) p x2
*n x pˆ x2 n x dx
0
2 n nx
L
2 nx pˆ x2 n x pˆ x pˆ x n x pˆ x i . cos
sin dx
L L L L
0
1 L 2nx
1 cos dx (using the results of Terminal Question 8)
2 0 L
2
1 L nx
L in 2 d nx 2 n 2 nx
x sin i cos i sin
2 2n L 0 L L dx L L L L
L
L
2 n 2 2 nx
So p x2 2 sin 2
dx (see the margin remark)
L L L
0
44
Unit 5 Simple One-dimensional Potentials-I
2 2 n 2 2 L 2n 22
L3 2 L2
k1 v1 10
For the given condition, 2.5. Hence, T
k2 v 2 12.25
2 2
PC or C e 2d 0.05P
2
E E V0 E E V0
14. R 0. 2
0.447
E E V0 E E V0
45
Block 2 Applications of Quantum Mechanics
For (see the margin remark) V0 8 eV , E 9.35 eV 9 eV
46
Unit 6 Simple One-dimensional Potentials-II
UNIT 6
SIMPLE ONE-DIMENSIONAL
POTENTIALS-II
Structure
6.1 Introduction 6.4 One-Dimensional Finite Potential
Expected Learning Outcomes Well
6.2 One-Dimensional Barrier Potential Solving the Schrödinger Equation
Solving the Schrödinger Equation Parity of the Eigen Functions
Reflection and Transmission Energy Eigen Values
Coefficient for E V0 Symmetric Infinite Potential Well
Reflection and Transmission 6.5 Summary
Coefficient for E V0 6.6 Terminal Questions
6.3 Applications of Quantum Tunnelling 6.7 Solutions and Answers The idea of quantum
Alpha Decay tunnelling was used by
Scanning Tunnelling Microscope George Gamow in 1928 to
explain -decay and by
Cockcroft and Watson in
6.1 INTRODUCTION 1932, in their experiment
In Unit 5 you have solved the time independent Schrödinger equation for a to split an atom at
energies forbidden by
free particle, a particle confined to a certain region of space and a step
classical physics. Over the
potential. You have seen that for a free particle you can have a continuous years several Nobel Prizes
spectrum of energies, whereas when the particle is localized to a small region, have been awarded for
you have a discrete energy spectrum. In general, whenever you solve the time research based on the
independent Schrödinger equation for a potential V(x), you will have either (i) idea of quantum
“bound” states with discrete energy values, or (ii) “unbound” states with tunnelling: to Cockcroft
and Watson in 1954, to
continuous energy values. In this unit we first solve the time independent
Esaki in 1973 for
Schrödinger equation for a particle incident on a potential barrier and then for
discovering tunnelling in
a particle in a finite potential well. semiconductors, also in
Just like a potential well tends to attract and localize a particle, a barrier, as the same year to Giaever
the name suggests, has a tendency to deflect particles. When a classical and Josephson for
tunnelling in
particle is incident on a barrier, it will cross the barrier if its energy is greater
superconductors and to
than the barrier potential. It will be reflected at the barrier if its energy is less Binnig and Rohrer in 1986
than the barrier potential. What about a quantum particle? Will it be reflected for the scanning tunnelling
or transmitted through the barrier? No matter what the energy of a quantum microscope. Since
particle is, because the matter wave associated with it is finite everywhere – tunnelling across potential
there is no region of space that is forbidden to a quantum particle. In Unit 5, barriers is a purely
quantum mechanical
while solving the step-potential problem also you have seen that there is a
phenomenon, it is also
finite probability of finding a quantum particle in a classically forbidden region. seen as an important
The phenomenon in which a quantum particle is transmitted through a success of quantum
potential barrier and penetrates into regions which are classically forbidden to theory.
it is called “quantum tunnelling”. Quantum tunnelling was first noticed in 47
Block 2 Applications of Quantum Mechanics
1927 by Friedrich Hund and since then it has been used to explain many
physical phenomena and has several important applications (read the margin
remark).
In Unit 5 you have seen how a particle confined to a one-dimensional box.
was modelled by a one-dimensional infinite potential well, in which the
probability of finding the box outside the well was exactly zero. A particle
rigidly confined by an infinite potential well is an idealization which does not
correspond to any real physical situation. Given sufficient energy, it is always
possible for a particle to escape the confines of a well. Hence, it is important
that we study the behaviour of a quantum particle in a finite potential well. The
important difference between the two systems is that in this case, even if the
kinetic energy of the particle in the well is less that the potential energy, there
is a finite probability of finding the quantum particle outside the well.
In Sec. 6.2 we solve the Schrödinger equation for the barrier potential and
calculate the reflection and transmission probabilities at the barrier. In
Sec. 6.3 we study some important applications of the concept of quantum
tunnelling in explaining -decay and in scanning tunnelling microscopy.
In Sec. 6.4 we solve the Schrödinger equation for the quantum particle in the
symmetric finite potential well. As you have studied, whenever a particle is
bound to a certain region of space, the energy spectrum is discrete and not
continuous. We learn how to calculate the energy eigenvalues and the
corresponding eigenfunctions. You will see that the eigenfunctions have a
definite parity which is a consequence of the symmetry of the potential
function. We also study the symmetric infinite potential well.
With this unit we complete our study of quantum mechanics. In the next block
you will study the fundamental concepts of nuclear physics.
Expected Learning Outcomes
After studying this unit, you should be able to:
solve the time independent one-dimensional Schrödinger equation for a
quantum particle incident on a potential barrier;
carry out calculations using the reflection and transmission coefficients;
identify the factors on which the tunnelling probability depends;
explain how tunnelling enables alpha decay;
describe the working of a scanning tunnelling microscope;
solve the time independent one-dimensional Schrödinger equation for the
finite potential well;
determine the eigenfunctions and energy eigenvalues for a particle in a
one-dimensional finite potential well;
determine the zero-point energy;
determine the eigenfunctions and energy eigenvalues for a particle in a
one-dimensional symmetric infinite potential well; and
state the parity of the stationary state wave functions.
48
Unit 6 Simple One-dimensional Potentials-II
V (x )
30 m
40 J 40 J V0
15 m
(a) (b)
I II III
Fig. 6.1: A ball having a kinetic energy of 40 J trying to cross a hump of height
a) 15.0 m; b) 30.0 m.
You have studied in Unit 5 that the function e ikx represents a particle moving
along the positive x-direction. And the function e ikx represents a free particle
moving along the negative x-direction.
In the expression for I (x ) , Ae ikx represents the plane wave that is incident
on the barrier at x 0 , which has an amplitude A and is travelling to the right.
Be ikx represents the plane wave reflected at the barrier, which has an
amplitude B and is moving towards the left from x 0 . So in Eq. (6.4) both A
and B are non-zero. In Region III, since there is only the wave that is
transmitted through the barrier and moving towards the right, and no wave
travelling to the left, we can set G 0 . So, the wave function for Region III is:
We next write the time independent Schrödinger equation for the particle in
Region II ( 0 x L ), where the wave function is denoted by II (x ) :
2 d 2 II ( x )
V0II ( x ) EII ( x ) (for Region II) (6.8)
2m dx 2
50
Unit 6 Simple One-dimensional Potentials-II
Let us now define a parameter k similar to k in Eq. (6.6):
2m(V0 E )
k (6.9)
2
Note that unlike in
Then we rewrite Eq. (6.8) as:
Eq. (5.7), in Eq. (6.11) we
d 2 II ( x ) 2m retain both the terms Ce k x
V0 E II ( x ) 0
dx 2 2 and De k x in the solution
or for region II. That is
d 2 II ( x ) because, in this case this
k 2 II ( x ) 0 (6.10) solution is valid only over
dx 2
the range 0 x L and
From your knowledge of homogeneous second order ODEs you know that the both terms in Eq. (6.11)
solution of Eq. (6.10) is (see the margin remark): would remain finite in this
range.
II ( x ) Ce k x De k x (for Region II) (6.11)
II ( x L ) III ( x L ) (6.14b)
And
d I ( x ) d II ( x )
(6.14c)
dx ( x 0 ) dx ( x 0 )
51
Block 2 Applications of Quantum Mechanics
d II ( x ) d III ( x )
(6.14d)
dx ( x L ) dx ( x L )
We first apply the boundary condition given by Eq. (6.14a). From Eq. (6.3) we
can write I ( x 0) A B . From Eq. (6.11) for II (x ) we get
II ( x 0) C D . Therefore, from Eq. (6.14a) we have:
AB C D (6.15a)
To apply Eq. (6.14b), we set x L in Eqs. (6.11 and 6.7) for II (x ) and
III (x ) , respectively, and get:
Ce k L De k L Fe ikL (6.15b)
To apply Eqs. (6.14c and d), we first write down the derivatives of I (x ) ,
II (x ) and III (x ) .
d I
dx
d
dx
Ae ikx Be ikx ik Ae ikx Be ikx (6.16a)
dII
dx
d
dx
Ce kx De kx k Ce k x De k x (6.16b)
d III
dx
d
dx
Fe ikx ik Fe ikx (6.16c)
Now we have four equations (6.15a and b, and 6.17a and b), but there are five
unknowns: A, B, C, D and F. However, as you will see in the next section, we
are interested in calculating the probability of reflection and transmission, for
which we need the ratios B / A and F / A . If we divide the equations (6.15a
and b, and 6.17a and b) by A, we will be left with just four unknowns as you
can see below:
C D B
1 (6.18a)
A A A
C k L D k L F ikL
e e e (6.18b)
A A A
C D B
k ik 1 (6.18c)
A A A
C D F
k e k L e k L ik e ikL (6.18d)
A A A
V (x )
V0
I (x )
II ( x ) III ( x )
I II III
x
x0 x L
Fig. 6.3: The wave function for the one-dimensional potential barrier for a
particle with an energy less than the barrier height.
In region III, the wave function is purely a travelling wave. We can calculate
the probability density of the wave in this region as:
P (x )
V0
I II III
x
x0 xL
Fig. 6.4: The probability density as a function of position, for a quantum
mechanical particle with an energy less than the barrier height.
53
Block 2 Applications of Quantum Mechanics
We next calculate the reflection and transmission coefficients which are a
measure of the probability of the particle being reflected or transmitted at the
barrier.
Ae ikx
incident
wave
Fe ikx
transmitted
wave
Be ikx
reflected
wave x
x 0 x L
As you have studied in Unit 5, the reflection coefficient is given by the ratio of
the magnitude of the probability current density associated with the reflected
wave to the magnitude of probability current density associated with the
incident wave (Eq. 5.59). So we write the reflection coefficient R as:
2
B
R (6.21)
2
A
You have studied that the intensity of a wave is proportional to its amplitude.
The reflection coefficient is, therefore, the fraction of the intensity of the
incident wave that is carried by the reflected wave. It also gives us the
probability that a particle having an energy E incident on a potential barrier V0
(such that E V0 ) is reflected back by the barrier.
This is the ratio of the intensity of the transmitted wave to the intensity of the
incident wave.
54
Unit 6 Simple One-dimensional Potentials-II
Since the incident wave is either reflected or transmitted, we must also have
the sum of the reflection and transmission coefficient to be one:
R T 1 (6.23)
To calculate R and T for the system we have to calculate B / A and F / A
using Eqs. (6.18 a to d). The algebra is lengthy but straightforward and is
worked out for you in the Appendix to this unit which you should work
through. We write down the results for T and R:
1
V0
2
T 1 sinh2 (k L ) (6.24a)
4E (V0 E )
1
4E (V0 E )
R 1 (6.24b)
2 2
V0 sinh (k L )
where
e k L e k L
sinh( k L ) (6.24c)
2
and
2mL2 (V0 E ) 2mV0 L2 E
k L 1 (6.24d)
2 2 V0
The transmission coefficient tells us about the extent of the penetration of the
barrier by the particle. It is also called the tunnelling probability.
Notice that Eq. (6.24a) tells us something that is totally at odds with classical
behaviour. For a classical particle, for E V0 , the particle is always reflected at
the barrier. So R = 1 and T = 0. But, for a quantum mechanical particle there is
always a small but finite probability for the particle to penetrate the barrier
and appear on the other side. This phenomenon is called “barrier
penetration”. You can see that the transmission coefficient becomes
vanishingly small in the limit of large values of k L , because the factor e 2 k L in
Eq. (6.24a) would be very small.
For large values of k L , sinh( k L ) e k L / 2 and we can write the expression for
the transmission coefficient as:
1
V0
2
e 2k L
T (6.25)
4E (V0 E ) 4
or
16E E
T 1 e 2k L for k L 1 (6.26)
V0 V0
Eq. (6.26) holds for wide barriers and large values of V0.
The transmission coefficient T decreases exponentially as e 2k L and T 1 .
The factor k L in the exponent (refer to Eq. 6.24d) is very large because
Planck’s constant is a very small number.
We define a tunnelling length:
1
T (6.27)
k 2m(V0 E ) 55
Block 2 Applications of Quantum Mechanics
T is a measure of the opacity of the barrier. It is also known as the barrier
penetration depth. At a distance T into the barrier, the wave function has
fallen to 1/e of its value at the barrier edge; thus, the probability of finding the
particle is appreciable only within about T of the barrier edge. Notice that T
decreases exponentially with L, the barrier width (beyond the tunnelling
length) and the energy difference (V0 E ) .
In terms of the tunnelling length, Eq. (6.26) can be written as:
2L
16E E L
T 1 e T for 1 (6.28)
V0 V0 T
Let us estimate how the transmission coefficient changes with the barrier width
L for a fixed value of the tunnelling length T .
Example 6.1
Consider an electron bound inside a typical metal. Typically the effective value
of (V0 E ) that prevents the electron from escaping the metal is ~ 5.0 eV.
Calculate the tunnelling length and the ratio of the transmission coefficients for
L= 0.3 nm and 0.2 nm.
.09 10 9 m .09 nm
Example 6.2
Calculate the transmission coefficient for an electron of energy 1.5 eV incident
on a potential barrier of 2.0 eV, if the width of the barrier is 0.50 nm.
Solution : We calculate first calculate T using Eq. (6.27) with
E 1.5 eV, V0 2.0 eV and then calculate the value of T from Eq. (6.26), with
1
using L = 0.50 nm and k . So,
T
T
1.054 10 34 Js
2 9.109 10 31 kg 0.80 10 19 J
0.28 10 9 m 0.28 nm
2L
E E T
T 16 1 e
V0 V0
2 0.50 nm
1.5 eV 1.5 eV 0.28 nm
16 1 e
2.0 eVV 2.0 eV
3e 3 . 6
SAQ 1
You should not take the word ‘tunnelling’ literally. There is, of course, a finite
probability for the particle to be inside the classically forbidden barrier region
where its kinetic energy is negative. But the point is that nobody can "see" a
particle actually go through a classically forbidden region.
Particle detectors can detect only objects of kinetic energy greater than zero.
Suppose you are able to tunnel through a barrier to insert a detector inside it
to ‘see’ the particle. Then, you are not only making a hole in the potential but
also in your objective. Why so? Because the object will no Ionger belong to a
classically forbidden region, where you wanted to find it! Another way to say
this is that our effort to observe the object with any measuring instrument will
give it an uncontrollable amount of energy. This is how the uncertainty
principle works in such measurement situations!
We now study the reflection and transmission coefficient for Case II in which
the energy of the particle E V0. 57
Block 2 Applications of Quantum Mechanics
6.2.3 Reflection and Transmission Coefficient for
E > V0
Let us write down the wave function for the three regions for E V0
(Eqs. 6.4, 6.12 and 6.5) once again:
I ( x ) Ae ikx Be ikx (for Region I) (6.3)
2m(E V0 ) 2mE
where and k .
2 2
You can see that the wave function is oscillatory in all three regions. Applying
the boundary conditions Eqs. (6.14a to d) at x 0 and x L for the wave
function and its derivatives as stated in Sec. 6.2.2, we can derive the
expressions for the transmission and reflection coefficients as:
1
V0 2
T 1 sin2 (L ) (6.29a)
4E (E V0 )
1
4E (E V0 )
R 1 (6.29b)
2 2
V0 sin (L )
From the expressions you can see that both R and T have an oscillatory
component. Notice here that even when E V0 , there is a finite probability for
the particle to be reflected at the barrier.
Once again this behaviour is NOT what is predicted by classical mechanics. A
classical particle which has an energy E V0 would be transmitted and not
reflected (T = 1 and R = 0).
The typical variation of the transmission coefficient with the ratio of the particle
energy E to the value of the potential at the barrier which is V0 , is plotted in
Fig. 6.6. For E / V 0 1 , T is defined by Eq. (6.24a) and for E / V 0 1 , T is
given by Eq. (6.29a). For E / V 0 1 , you can that while there is a finite
probability of tunnelling , R T .
T
E /V0
Fig. 6.6: The typical variation of the reflection coefficient R and transmission
2mV0 L2
coefficient T with E /V0 , for 16 .
58 2
Unit 6 Simple One-dimensional Potentials-II
Notice that the value of T is close to 1 for E V0 and actually equal to 1 at
some points. These are the points at which T = 1 in Eq. (6.29a) and so we
must have:
sin 2 (L ) 0 L n for n 1,2,3... (6.30)
All alpha particles emitted from the same source have almost the same
kinetic energy. If they are emitted from different sources, the kinetic
energies all lie within a narrow range of 4.0 to 9.0 MeV.
The half-life of the radioactive element from which the alpha particle is
emitted, however varies over a very large range: for example the half-life
for polonium-214 is 160 s and the half life of uranium-238 is around
4.5 billion years. Incidentally the kinetic energies of the emitted alpha
particles are ~7.7 MeV for polonium and 4.3 MeV for uranium.
This large variation in the half-lives of the parent element in the alpha decay
process was explained by George Gamow using the concept of quantum
tunnelling. He assumed that before the alpha decay takes place, an alpha
particle exists inside the parent nucleus and is bound by the attractive
potential of the strong nuclear force. You may consider the nucleus to be a
kind of rigid spherical box inside which the alpha particle is confined. The
alpha particle is free to move between the walls of the box. It does have a
finite kinetic energy but this kinetic energy is much less that what required to
escape from the nucleus, leaving behind the daughter nucleus. So classically,
the alpha particle should remain forever remain bound inside the parent
nucleus.
Ze (2e ) Ze 2
V (r ) (6.31)
4 0 r 2 0 r
The shaded region shows the forbidden region for the alpha – particle.
V (r )
Ze 2
V (r )
20r
E
r
R
R0
The kinetic energy of the alpha particle is E. At the point R, at which the alpha
particle escapes the nucleus, the kinetic energy of the alpha particle is at least
equal to the electrostatic energy between it and the daughter nucleus. So,
at r R ,
Ze 2
E (6.32)
2 0 R
Electrons tunnelling
between the sample
surface and the tip
sample tip
surface
Note that the well defined by Eq. (6.34) has the following features:
The potential energy V0 is finite for x a as well as for x a .
The potential energy is zero for a x a .
The potential function V (x ) is symmetric, i.e. V ( x ) V ( x )
V V0
V0
I II III
V=0
x a x
0 x a
Fig. 6.9: A one-dimensional finite potential well. The potential energy is V0 for
x a (Region I) and for x a (Region III). It is zero for
a x a (Region II).
If the total energy (E) of a classical particle is greater than the barrier height
V0 , it can move freely in the entire region, including the region x a and
x a . Its kinetic energy would be E V0 in the region x a and x a and E
in the region a x a . However, if E is less than V0 , the classical particle
would remain bound forever in the region a x a . It would move back and
forth in the region with a constant speed (and a momentum of constant
magnitude) and the total energy of the particle could have any value E 0 .
62 Quantum mechanically, however, a bound particle can only have certain
Unit 6 Simple One-dimensional Potentials-II
discrete values of the energy. Further, as you have also seen in Unit 5, there
is a finite probability for the quantum mechanical particle to penetrate the
classically forbidden region i.e., x a as well as x a even if its
energy E V0 .
2 d 2 ( x )
E ( x ) (for Region II) (6.35)
2m dx 2
Inside the well we have a free particle. You already know the solution of the
Schrödinger equation for a free particle (Eq. 5.23). It is:
II ( x ) A sin kx B cos kx (for Region II: a x a ) (6.36)
2mE
k (6.38)
2
We next write the time independent Schrödinger equation for the particle in
Regions I and III ( x a and x a , respectively) which is:
2 d 2 ( x )
V0 ( x ) E ( x ) (6.39)
2m dx 2
You have learnt how to solve such an equation in Unit 5 and Sec. 6.2. We
define a parameter k :
2m(V0 E )
k (6.40)
2
63
Block 2 Applications of Quantum Mechanics
We can rewrite Eq. (6.39) as:
d 2 ( x ) 2m
V0 E ( x ) 0
dx 2 2
d 2 ( x )
or k 2 ( x ) 0 (6.41)
dx 2
Let us write the solution for this equation for Regions I and III separately
(recall Eq. 6.10 and 6.11) where the wave functions are I (x ) and IIl (x ) ,
respectively:
I ( x ) Ce k x De k x (for Region I : x a) (6.42)
And
III ( x ) Fe k x Ge k x (for Region III : x a) (6.43)
Let us consider that the total energy of the particle E V0 . Therefore, V0 E
is positive and the parameter k is real. We know that an acceptable wave
function must be finite for all values of x. Since the term De k x in Eq. (6.41)
diverges as x and the term Ge k x in Eq. (6.42) diverges as x , for
the wave function be finite in all regions we must have :
D G 0 (6.44)
and
Now
2 d 2 ( x )
Hˆ ( x ) V ( x )( x ) (iii)
2m dx 2
In Unit 4 you have studied that the parity operator is the space inversion operator
( x x ) and Pˆ ( x ) ( x ) . So the first term on the RHS of
Eq. (ii) is:
2 d 2 ( x )
Pˆ Hˆ ( x )
2m dx 2
V ( x )( x )
2 d 2 ( x )
V ( x )( x ) [since V ( x ) V ( x )]
2m dx 2
2 d 2
V ( x ) ( x ) Hˆ ( x ) (iv)
2m dx 2
Let us now apply this property to the potential function in Eq. (6.34).
6.4.2 Parity of the Eigenfunctions
Recall that the finite well potential function defined by defined by Eq. (6.34) is
symmetric, that is V ( x ) V ( x ) . So, as you have learnt by solving
Example 6.3, the Hamiltonian Ĥ of the symmetric potential well commutes
with the parity operator P̂ .
Now recall another result from Example 4.9 of Unit 4: If an operator Â
commutes with the parity operator P̂ , then the non-degenerate eigenfunctions
of  have a definite parity, i.e., they are either of odd parity or of even parity.
So the solutions of the Schrödinger equation for the symmetric finite potential
well, which are the eigenfunctions of Ĥ , will have a definite parity. That is: the
eigenfunctions will either be even or odd.
Now this helps us to simplify the wave function for Region II given by
II ( x ) A sin kx B cos kx .
Notice that this wave function does not have a definite parity because sin kx is
an odd function [ sin k ( x ) sin kx ] and cos kx is an even function
[ cos k ( x ) cos kx ]. We have already established that the wave function
must have a definite parity. Therefore, either A or B should be zero.
If we take A = 0 we get even parity solutions:
II ( x ) B cos kx (even parity : ( x ) ( x ) ) (6.47)
Both solutions are valid. Now let us apply the boundary conditions. The wave
functions must match at the boundaries of the potential well and so the
boundary conditions are:
I ( x a ) II ( x a ) (6.49a)
and
II ( x a ) III ( x a ) (6.49b)
Let us first work out the relation between the constants for the even parity
solution: II ( x ) B cos kx . Substituting x a in Eqs. (6.45 and 6.47), we
get from Eq. (6.49a):
Ce k a B cos k ( a ) B cos ka (6.50)
Since e k a 0 , the following must be true for the even parity solution:
C F (6.53)
For the odd parity solution, II ( x ) A sin kx using Eqs. (6.49a and b)
respectively we get:
C F (6.54)
You can verify Eq. (6.54) for yourself by solving SAQ 2.
SAQ 2
Now we can write the complete set of solutions for the finite potential well.
The even parity solutions are (using C F ):
I ( x ) Ce k x (for x a ) (6.55a)
II ( x ) B cos kx (for a x a ) (6.55b)
I ( x ) Ce k x (for x a ) (6.56a)
d( x )
You know that for (x ) to be an acceptable wave function, (x ) and
dx
should be continuous for all x. Therefore the derivative of the logarithm of
(x ) which is
d
ln ( x ) 1 d( x ) , should also be continuous. We now
dx ( x ) dx
write the condition of continuity for the derivatives of ln ( x ) at the boundary of
Regions I and II:
1 d I ( x ) 1 dII ( x )
(6.57)
I ( x a ) dx x a II ( x a ) dx x a
Since
d I
dx
d
dx
Cek x Ck e k x (6.58)
dII d
Bk cos kx B sin kx (6.59)
dx dx
On imposing the condition given by Eq. (6.57) on the even parity solution, we
get for x a :
1 1
Ck e k a Bk sin ka k k tan ka (6.60)
Ce k a B cos ka
2m(V0 E )a 2 2mEa 2
k a and ka (6.62)
2 2
Notice that and are dimensionless quantities, but both and are
functions of the energy of the particle E.
2m(V0 E )a 2 2mEa 2
2 2 k a 2 ka 2
2 2
2mV0a 2
R2 (6.63)
2
67
Block 2 Applications of Quantum Mechanics
where R is a constant that depends on the depth of the well ( V0 ) and its width
2a:
2mV0 a 2
R (6.64)
2
The energy eigenvalues can now be obtained by solving Eqs. (6.61) and
(6.63) for and for a fixed value of R. Combining these equations we can
write:
Before we solve these equations you can derive the conditions equivalent to
Eq. (6.65a) for the odd parity states.
SAQ 3
Show that for the odd parity solutions given by Eqs. (6.56 a,b,c) the boundary
conditions on the continuity of the derivatives of the wave function lead to the
following conditions:
Eqs. (6.65a and 6.65b) are Eq. (6.65 a and b) are solved graphically as shown in Fig. 6.10. For this, we
what are known as plot along the x-axis and along the y-axis. Since both and are greater
transcendental than zero, we plot only the first quadrant. The equation 2 2 R 2
equations, where the
represents a circle with a radius R and is plotted in Fig. 6.10 for four different
variable appears both as
an argument to a values of R. For each value of R (corresponding to the value of the product
transcendental function V0 a 2 ), we get a different circle.
and elsewhere in the
equation. These equations
A
tan B
are not solvable in closed cot
form. So we have to solve C
them numerically or R 6 .2
graphically
R 3 / 2 D
R 2 2
R
R /2
Fig. 6.10: Graphical Solution of Eqs. 6.65a and b. The red, blue and black
curves represent the functions tan , cot and
2 2 R 2 respectively.
The equation tan and cot are plotted by the red and blue lines
respectively in Fig. 6.10. The solutions of Eq. (6.65a) are the points at which
the plot of the function 2 2 R 2 and tan intersect. In Fig. 6.10, for
R 6.2 , these points of intersection are A and C. At any point of intersection
68
Unit 6 Simple One-dimensional Potentials-II
we get a value of , say n . This value of n can be used to calculate the
2 n 2
energy eigenvalue E n using the relation En (from Eq. 6.62).
2ma 2
Remember that this is for a particular value of R.
The solutions of Eq. (6.65b) are the points at which the plot of the function
2 2 R 2 and cot intersect, which are the points B and D in
Fig. 6.10 for R 6.2 . Once again, at the point of intersection, we can calculate
the energy eigenvalue using Eq. (6.62).
Note from Fig. 6.10 that the allowed values of and hence E are discrete and
the number of allowed values of E increases as R increases. The solutions of
Eq. (6.65a) give us the energy eigenvalues for the even parity states and the
solutions of Eq. (6.65b) give us the energy eigenvalues for the odd parity
states.
Therefore for E V0 , the energy levels of a particle in a finite potential well are
discrete and depend upon the well parameters ( V0 ) and its width a. From
Fig. 6.10, note that:
For a value of R lying between 0 and /2, there is just one possible
solution of the set of Eqs. (6.65a and b) and that corresponds to a state of
even parity (obtained from the intersection of the curves 2 2 R 2 and
tan ). We can write:
2 22
R R2 V0 a 2
2 4 8m
22
So for 0 V0 a 2 you can have just one bound state of even
8m
parity. There are no odd parity states for a value of R between 0 and /2.
The number of bound states depends on the value of R. The greater the
value of R (larger the value of V0 ), the greater the number of bound
states. As the value R increases, more bound states of even and odd
parities get added to the eigenfunctions.
For the value of R = 6.2, you can see that there are four bound states. The
first intersection is at A, corresponds to a value of 1 and it gives us
the ground state energy for R 6.2 . It is a state of even parity. The next
intersection is at B, which corresponds to 2 and gives us the energy
of the first excited state, and so on.
Clearly, for E V0 the particle is bound to the well and the energy spectrum is
discrete. What if the energy of the particle is greater than V 0 ?
In that case the particle is no longer confined to the well and the energy of the
particle varies continuously from V0 to .
In Fig. 6.11, you can see typical energy level diagram for a particle in a finite
potential well. For E V0 , , you have discrete energy levels. For E V0 , you
have a continuum of energies. Continuum
of Energies
V V0 V V0
E3
Discrete
E2 energy
levels
E1
x = a x=a
Fig. 6.11: Typical energy eigenvalues for a finite potential well.
for x a
V ( x ) 0 for a x a (6.66)
for x a
where we have replaced V0 by in Eq. (6.1). Recall that we have solved the
infinite potential well in Unit 5. However, the potential well we studied in Unit 5
was not symmetric about x 0 .
Since there is an infinite potential for x a and x a , we can say that the
wave function will not extend beyond the boundaries of the well. Therefore, for
both the even and odd parity solutions:
I ( x ) III ( x ) 0
70 And for a x a , we can write for the infinite symmetric potential well:
Unit 6 Simple One-dimensional Potentials-II
Even Parity Solution : ( x ) A cos kx (for a x a ) (6.67a)
The constants A and B are determined by the normalization condition for the
wave function. We can also write the following boundary condition for the
wave function going to zero at the boundaries of the potential well:
( x a ) ( x a ) 0 (6.68)
The corresponding eigen energy for the even parity states is found using
2k 2
E and the value of k as obtained in Eq. (6.69):
2m
2 n 2
E n,even with n 1,3,5,.... (6.70b)
2m 2a
You can obtain the corresponding odd parity eigenfunctions and the eigen
energies by applying Eq. (6.68) to Eq. (6.67b). You may like to work this out
for yourself.
SAQ 4
Show that the odd parity eigenfunctions and eigen energies of the symmetric
infinite potential well are:
nx
odd ( x ) B sin with n 2,4,6.... (6.71a)
2a
and
2 n 2
E n,odd with n 2,4,6.... (6.71b)
2m 2a
You can see for yourself that the lowest possible energy is for n 1 in
Eq. (6.70b) which is:
22
E1 (6.72a)
8ma 2
x
This corresponds to the even parity eigen function 1( x ) A cos . This is
2a
the ground state and this energy is the zero point energy. Notice that the
minimum energy is not zero.
So as you can see, the eigenfunctions are alternately of even and odd parity.
Now that we know the form of the eigenfunctions for the infinite potential well,
we can deduce what the eigenfunctions of a finite potential well would look
like. Unlike in the infinite potential well, the wave function for a finite potential
well would not go to zero at the boundaries of the potential well. Rather the
wave function would decay exponentially on both sides of the potential well
and the form of the wave function is given by I ( x ) and III ( x ) as described in
Eqs. (6.55a and 6.55c) or Eqs. (6.56a and 6.56c) depending on the parity of
the solution.
In Fig. 6.12(a) and (b) we plot the first three eigenfunctions for the infinite and
finite symmetric potential well respectively.
V V0 V (x ) V V0
V V (x ) V
3(x) 3(x)
2(x) 2(x)
1(x) 1(x)
x x
x = a 0 x=a x = a 0 x=a
(a) (b)
Fig. 6.12: The first three eigenfunctions for (a) a symmetric infinite potential
well, and (b) a symmetric finite potential well
Note that the wave function extends into the classically forbidden region on
either side of the boundary of the finite potential well.
We define what is known as the penetration depth, which is the distance to
which the wave function penetrates the region beyond the boundaries of the
potential as:
1
(6.73)
k 2m(V0 E )
72
Unit 6 Simple One-dimensional Potentials-II
At a distance beyond the boundary of the well the amplitude of the wave
function falls to 1/e of its value at the boundary. At this distance, the wave
function in the exterior of the well is almost zero.
Also the eigen energies for a finite well are typically less than that for an
infinite square well of the same width. This is because when the wave
functions extend upto a distance of beyond the boundaries of the well, we
can say that the effective size of the box increases. So the typical energies are
lower.
6.5 SUMMARY
The potential energy function for a one-dimensional potential barrier of
width L is:
0 for x 0
V ( x ) V0 for 0 x L
0 for x L
II ( x ) Ce k x De k x (for 0 x L )
where
2mE 2m(V0 E )
k and k
2 2
The transmission coefficient T is the probability of a particle being
transmitted through the barrier and is given by:
1
V0 2
T 1 sinh2 (k L )
4E (V0 E )
where
73
Block 2 Applications of Quantum Mechanics
1
4E (V0 E )
R 1
V02 sinh2 ( k L )
1
T
k 2m(V0 E )
The wave function for the three regions for E>V0 are:
2m(E V0 ) 2mE
where and k .
2 2
1
4E (E V0 )
R 1
V0 2 sin 2 (L )
I ( x ) Ce k x (for x a )
II ( x ) B cos kx (for a x a )
III ( x ) Ce k x (for x a )
The odd parity solutions for E V0 are:
I ( x ) Ce k x (for x a )
II ( x ) B sin kx (for a x a )
III ( x ) Ce k x (for x a )
The energy eigenvalues can be obtained by solving the transcendental
equations:
2 2 R 2 ; tan ; , 0 for even parity states
2 2 R 2 ; cot ; , 0 for odd parity states
for and for a fixed value of R, where
2m(V0 E )a 2 2mEa 2 2mV0 a 2
k a ; ka ;R
2 2 2
For E V0 the particle is bound to the well and the energy spectrum is
discrete.
The lowest energy state is always an even parity state and there is
always at least one bound state. 75
Block 2 Applications of Quantum Mechanics
The number of bound states depends on the radius of the circle, R.
The greater the value of R (larger the value of V0 ), the greater the
number of bound states.
The potential function for the symmetric one-dimensional infinite potential
well is
for x a Region I
V ( x ) 0 for a x a Region II
for x a Region III
The solutions of the Schrödinger equation for a particle of mass m in the
symmetric infinite well have a definite parity:
nx
even ( x ) A cos with n 1,3,5,....
2a
nx
odd ( x ) B sin with n 2,4,6....
2a
The eigen energies are:
2 n 2
E n,even with n 1,3,5....
2m 2a
2 n 2
E n,odd with n 2,4,6,.... \
2m 2a
22
The ground state energy is: E1
8ma 2
i) when the width of the barrier is reduced to 0.4 nm, other parameters
remaining the same.
5. An electron has a kinetic energy of 8.0 eV. The electron is incident upon a
rectangular barrier of height 15.0 eV which has a thickness of 1.0 nm.
Calculate the increase in the tunnelling probability of the electron if it
76 absorbs all the energy of a photon of blue light (3.1eV).
Unit 6 Simple One-dimensional Potentials-II
6. Calculate the probability that an electron will tunnel through a 0.4nm gap
from a metal to the STM probe if the work function is 3.0eV. By what factor
does the tunnelling probability change if we increase the gap to 0.50 nm.
p2 1
H m2 x 2
2m 2
8. Calculate the normalization constants for the wave functions of
Eqs. 6.34a and b.
i) ( x ) A cos kx (for a x a )
10. The penetration depth for an electron is 2.0 nm. How much energy would
be required to “free” the electron from the well?
1.054 10 34 Js
T
2 0.22 9.109 10 31 kg 0.80 10 19 J
0.58 nm (i)
E 1.5 eV 3
Using Eq. (6.28) with , L 0.10 nm , and T as calculated
V0 2.0 eV 4
in Eq. (i) we calculate the transmission coefficient T :
20.10 nm
3 3
T 16 1 e 0.58 nm 3 e 0.34
4 4
2. We use the condition given in Eq. (6.49a), with ll x A sin kx to get,
A sin ka Fe k a (ii)
e k a 0 we must have C F
k k cot ka (iv)
or k a ka cot ka (v)
So, we can write the conditions for odd parity states as:
2 2 R 2; cot , , 0
B sin ka 0 sin ka 0 or ka n , n 2,4,6,...
2
n
k , n 2,4,6,...
2a
nx
So n ( x ) B sin , n 2,4,6,...
2a
2k 2 2 n 2
And En , n 2,4,6,...
2m 2m 2a
Terminal Questions
1. We first calculate the tunnelling length T using Eq. (6.27) with
E 4.0 eV,V0 10 .0 eV and m m e :
1.054 10 34 Js
T 0.08 nm (i)
2 9.109 10 31 kg 9.6 10 19 J
E 4.0 eV 2
With , L 0.80 nm and T 0.8 nm in Eq. (6.28):
V0 10.0 eV 5
20.80 nm
2 2
T 16 1 e 0.08 nm
96 20
e 3.84 e 20
5 5 25
2. Let us denote the transmission coefficient calculated in TQ 1 by T 0 . So
78
Unit 6 Simple One-dimensional Potentials-II
E 2
i) With L = 0.40 nm, T 0.08 nm and in Eq. (6.28) :
V0 5
20.40 nm
2 2
T1 16 1 e 0.08 nm 3.84 e 10 (ii)
5 5
ii) We first calculate T with E 8.0 eV, V0 10 eV and m m e
T
1.054 10 34 Js 0 .14 nm
2 9.109 10 31 kg 3.2 10 19 J
E 8.0 eV 4
Then with E = 8 eV , L = 0.80nm, and
V0 10 .0 eV 5
T 0.14 nm, we get from Eq. (6.28):
2 0.80 nm
4 4
T2 16. 1 e 0.14 nm
5 5
64 11.4
e ( 2.56 )e 11.4 (iii)
25
We now calculate the ratios of the transmission coefficients T1 and T2
with respect to T0 :
T1 (3.84 )e 10
e10
T0 (3.84 )e 20
T2 (2.56 ) e 11.4
and (0.67 ) e 8.6
T0 (3.84 ) e 20
Since e 10 0.67e 8.6 we can say that the tunnelling probability increases
more in case (i) when width of the barrier is decreased.
3. Let us say that the tunnelling length for the electron is
TE
2me V0 E
And the tunnelling length for the proton ( m P 1836 m e ) is
TP
2mP V0 E
21836me V0 E 2me V0 E 1836
Te (i)
43
The transmission coefficient for the electron is
2L
E E
Te 16 1 e Te
V0 V0
and for the proton it is:
79
Block 2 Applications of Quantum Mechanics
2L
E E TP
T P 16 1 e
V 0 V0
2L 2L
2L
Te e Tee Te
42
e Te Te TP
TP 2L 2L
e Tp e Te 43
So T
1.054 10 34 Js 0.14 nm
2 9.109 10 31 kg 3.2 10 19 J
(i)
The tunnelling probability is calculated using Eq. (6.28) with
E 8 eV 4 1
and T 0.14 nm . Given that T 2% we can
V0 10 eV 5 50
write:
2L
1 4 4
T 16 1 e 0.14 nm
50 5 5
2L 2L
25
e 0.14 nm or e 0.14 nm 128
64 50
Taking the logarithm of both sides,
2L
ln128 L 0.07 4.85 nm 0.34 nm
0.14 nm
5. We first calculate the tunnelling length using Eq. (6.27), with
V0 E 15.0 8.0 eV 11.2 10 19 J
1.054 10 34 Js
T
2 9.109 10 31 kg 11.2 10 19 J
0.074 10 9 m 0.074 nm (i)
The tunnelling probability T1 is calculated using Eq. (6.28) with L = 1.0 nm,
8.0 eV 1
E / V0 and T 0.074 nm
15.0 eV k
2 1.0 nm
8 8
T1 16 1 e 0.074 nm ( 4.0)e 27 (ii)
15 15
When electron absorbs an photon of energy 3.1eV its kinetic energy
becomes
1.054 10 34 Js
T
2 9.109 10 31 kg 6.24 10 19 J
0.098 nm (iii)
80
Unit 6 Simple One-dimensional Potentials-II
11.1
With E / V0 and T given by Equation (iii) the tunnelling probability
15.0
is:
21.0 nm
11.1 11.1 .098 nm
T2 16 1 e 3.1 e 20.4
15.0 15.0
1.054 10 34 Js
T 0.11nm
2 9.109 10 31 kg 4.8 10 19 J
Given that E ,V0 are fixed we can write that the tunnelling probability is a
function only of the gap between the tip of the STM probe and the surface
i.e. T f E / V0 e 2L / T .
T2 f E / V0 e 9.1 1
e 1.8
T1 f t / V0 e 7 . 3 6
where
d2 1
Hˆ 2 m2 x 2
dx 2 2
So 2 d 2 1
Pˆ Hˆ x Pˆ
m2 x 2 x
dx 2 2
81
Block 2 Applications of Quantum Mechanics
d x
2
1
2 m 2 x 2 x (ii)
2 2
dx
and
Hˆ Pˆ x
2 d 2 ( x ) 1
m 2 x 2 x (iii)
2m dx 2 2
or Pˆ , Hˆ 0
the parity operator commutes with the Hamiltonian, the eigenfunctions will
have a definite parity.
8. i) The normalization condition is
a a
n
x x dx 1 A
* 2
a
cos2 kx dx 1 where k
2a
(n 1,3,5...)
a
a
A2 A2 1 a
1
2 1 cos 2 kxdx 1 2
x
2k
sin 2kx
a
a
Given that
n n
k ( n 1,3,5...) sin 2ka sin 2 a sin( n) 0
2a 2a
A2 1
2a 1 and A A
2 a
ii) The normalization condition is written as
a
n
B2 sin2 kx dx 1 where k 2a , n 2,4,6...
a
a
B2
2 1 cos 2 kx dx 1
a
B2 1
a
or x sin 2 kx 1
2 2k
a
B2 2a 1 sin 2ka 1
or
2 2k
2n
sin 2ka sin a sin n 0
2a
B2 1
2a 1 or B B
2 a
9. We calculate penetration depth using Eq. (6.73).
82
Unit 6 Simple One-dimensional Potentials-II
With V0 100 eV and E 40 eV
1.054 10 34 Js
So
2 9.109 10 31 kg 60 1.6 10 19 J
.025 10 9 m .025 nm
10. The energy required to free the electron is V0 E .
V0 E
2 (i)
2me 2
we get,
V0 E
1.054 10 34 Js2 0.015 10 19 J
2 9.109 10 31 kg 2.0 10 9 m
2
0.01eV
83
Block 2 Applications of Quantum Mechanics
APPENDIX 6A: CALCULATING THE REFLECTION AND
TRANSMISSION COEFFICIENTS
After applying the boundary conditions on the wave functions and their
derivatives for E V0 , we have derived the following equations for A, B, C, D
and F:
AB C D (6.15a)
e k LC e k L D e ikL F (6.15b)
Let us first calculate the value of B/A from these equations. For this we
eliminate the constants C and D from the Eqs. (6.15a,6.15b, 6.17a and 6.17b).
Multiplying Eq. (6.15a) by k we get:
k A k B k C k D (i)
( k ik ) A ( k ik )B 2k C (ii)
( k ik ) A ( k ik )B 2k D (iii)
( k ik )e k LC ( k ik )e k LD
(k ik )e k L
or C D (vi)
( k ik )ek L
Eq. (vi) gives us the relation between C and D. Substituting for C from Eq. (vi)
into Eq. (ii) we get:
(k ik )ek L
(k ik )A (k ik )B 2k D
(k ik )ek L
which is:
(k ik )ek L
(k ik )A (k ik )B 2k D (vii)
(k ik )e k L
84
Unit 6 Simple One-dimensional Potentials-II
You can see that the RHS of Eqs. (iii) and (vii) are equal. Equating the LHS of
these two equations we get:
(k ik )e k L
(k ik )A (k ik )B
(k ik )e k L
( k ik ) A ( k ik )B (viii)
On simplifying, we can write Eq. (viii) as:
(k ik )e k L (k ik )A (k ik )B
(k ik )e k L (k ik )A (k ik )B Notice that B/A given in
which is: Eq. (xii) is complex and it
has the general form:
(k ik )(k ik )e k L A (k ik ) 2 e k L B
B u
( k ik )(k ik )e k L A ( k ik )2 e k L B
A v iw
Using ( k ik )(k ik ) k 2 k 2 we can write:
u v iw
(k 2 k 2 )e k L A (k ik ) 2 e k L B
v iw v iw
(k 2 k 2 )e k L A (k ik )2 e k L B (ix) uv iuw
Dividing Eq. (ix) by A we get v2 w2
B
(k 2 k 2 )e k L (k ik ) 2 e k L
A B
2
uv 2 uw 2
(k 2 k 2 )e k L (k ik )2 e k L
B
(x)
A v 2 w 2 2
A
u 2 v 2 w 2
Therefore we have
B
( k 2 k 2 )e k L e k L
(xi)
v 2 w 2 2
A ( k ik ) 2 e k L ( k ik ) 2 e k L u2
which is:
v2 w2
B
(k 2
k 2 ) e k L e k L
(xii) With :
A ( k k )e
2 2 k L e k L (2ik k )e k L e k L
u ( k 2 k 2 ) sinh(k L )
or
v ( k 2 k 2 ) sinh( k L )
B ( k 2 k 2 ) sinh( k L )
(xii) And
A ( k 2 k 2 ) sinh( k L ) 2ik k cosh( k L )
w 2k k cosh(k L)
B2
The reflection coefficient is R (Eq. 6.21). Using the value of B/A We get the result of
A2 Eq. (xiii).
obtained in Eq. (xii) we can write (see the margin remark):
( k 2 k 2 ) 2 sinh 2 ( k L )
R (xiii)
( k 2 k 2 ) 2 sinh 2 ( k L ) 4k 2 k 2 cosh 2 ( k L )
Using the identity sinh2 (k L) cosh2 (k L) 1 , we can simplify the denominator
of the RHS of Eq. (xiii) as
(k 2 k 2 ) 2 sinh 2 (k L ) 4k 2 k 2 cosh 2 (k L )
( k 2 k 2 ) 2 sinh 2 ( k L ) 4k 2 k 2 sinh 2 ( k L )
4k 2k 2 cosh2 (k L ) 4k 2k 2 sinh2 (k L )
(k 2 k 2 )2 sinh2 (k L ) 4k 2 k 2
Therefore
( k 2 k 2 ) 2 sinh 2 ( k L )
R
( k 2 k 2 ) 2 sinh 2 ( k L ) 4k 2 k 2
1
(k 2 k 2 )2 sinh 2 (k L ) 4k 2k 2
(xiv)
( k 2 k 2 )2 sinh 2 (k L ) 85
Block 2 Applications of Quantum Mechanics
2mE
From Eqs. (6.6 and 6.9) we also know that k and
2
2m(V0 E )
k .
2
2mE 2m(V0 E )
So, k2 ; and k 2
2 2
and
2m(V0 E ) 2mE 2mV0
k 2 k 2 ;
2 2 2
2m(V0 E ) 2mE
k 2k 2 (xv)
2 2
Substituting from Eq. (xv) into Eq. (xiv) we get the result of Eq. (6.24b):
1 1
4k 2k 2 4E (V0 E )
R 1 1
2 2 2 2 2 2
(k k ) sinh (k L ) V0 sinh (k L )
To calculate T we use Eq. (6.23). Hence T = 1 R. Using the value of R from
Eq. (xiv) we get:
( k 2 k 2 ) 2 sinh 2 ( k L )
T 1 R 1
( k 2 k 2 ) 2 sinh 2 ( k L ) 4k 2 k 2
4k 2 k 2
( k 2 k 2 )2 sinh 2 ( k L ) 4k 2k 2
1
(k 2 k 2 ) 2 sinh 2 (k L)
1 (xvi)
4k 2 k 2
Substituting from Eq. (xv) into Eq. (xvi) we get the following result of
Eq. (6.24a):
1
V 2 sinh 2 (k L )
T 1 0
4E (V0 E )
86
Unit 7 Simple Harmonic Oscillator-I
UNIT 7
SIMPLE HARMONIC
OSCILLATOR-I
Structure
7.1 Introduction Comparison with the Classical
Expected Learning Outcomes Oscillator
7.2 Stationary State Schrödinger Examples of Simple Harmonic
Equation Oscillator Systems
Power Series Solution 7.3 Solution with Ladder Operators
Boundary Conditions and 7.7 Summary
Eigenfunctions 7.5 Terminal Questions
Energy Eigenvalues 7.6 Solutions and Answers
Parity of the Eigenfunctions
Solution of the Time-Dependent
Schrödinger Equation
7.1 INTRODUCTION
Continuing with our study of one-dimensional quantum mechanical systems,
we now study a quantum particle in a parabolic potential. The system is one
that you are all familiar with – the one-dimensional harmonic oscillator or the
simple harmonic oscillator. The system is of direct physical interest, because a
large number of systems are governed exactly or approximately by the
harmonic oscillator equation.
F
The prototype of a classical one-dimensional harmonic oscillator is a mass m
connected to a spring, undergoing to and fro motion (Fig. 7.1). The motion m
follows Hooke’s law according to which the force F on the particle is directly x
proportional to the displacement and is always directed towards the mean x 0
position, i.e., F kx : k , the constant of proportionality, is known as the force Fig. 7.1: Mass on a
constant or the spring constant. It is related to the classical frequency of the spring as a one-
dimensional
oscillator and is given by k 42 2 m where m is the mass of the particle.
harmonic oscillator.
1
The potential energy of the particle at x is given by V ( x ) kx 2 or
2
1
V ( x ) m2 x 2 , where 2 is the angular frequency. If you plot the
2
potential V (x ) as a function of x, you will get a parabola, centred at x 0 .
The potential energy function for any arbitrary physical system may not be
perfectly parabolic. Yet, in the neighbourhood of a local minimum, almost any
87
Block 2 Applications of Quantum Mechanics
potential function can be approximated by a parabola. Consider the
potential function V (x ) of Fig. 7.2.
V (x )
x
xa
Fig. 7.2: A Potential Function V(x).
SAQ 1
Show that for a 2 m / and E , Eq. (7.3) reduces to
2
d 2 ( )
( 2 ) ( ) 0
d 2
We now determine the solution of Eq. (7.4) to get the eigenfunctions and
eigenvalues of the one-dimensional harmonic oscillator.
Before we obtain the solution using the power series method, we examine Eq.
(7.4) in the limits of large and small values of to obtain a trial solution.
In the limit , we can drop the term in comparison to 2 in Eq. (7.4)
89
Block 2 Applications of Quantum Mechanics
d 2()
to get the equation : 2() 0 . You can check for yourself that
d 2
2
( ) C m e / 2 is a solution of this equation. Since a physically acceptable
wavefunction should not diverge, we can drop the term with the positive
exponent term and retain only the negative exponent term to write the solution as
2
() Cme / 2 .
So we get:
1
d dh 2
h e 2 (7.6a)
d d
And
1
d 2 d 2h dh 2
2 (2 1)h e 2 (7.6b)
d 2 d 2 d
Substituting from Eq. (7.6b) into (7.6a) we get a differential equation for
h h( ) :
d 2h dh
2 ( 1)h 0 (7.7)
d 2 d
We solve this equation using the power series method by assuming a solution
for h() of the form:
90
Unit 7 Simple Harmonic Oscillator-I
h() cn n (7.8a)
n 0,1,2,...
We can write down the first and second order derivatives of h() as:
dh
d n 0,1,2..
cn n n 1 (7.8b)
d 2h
d2 n 0,1,2...
c n (n )(n 1) n 2 (7.8c)
(7.9)
We can also write Eq. (7.9) as:
cn 2 (n 2) (n 1) n 2 cn (n ) n ( 1)
n 0,1,2,... n 0,1,2,..
cn n 0 (7.10)
n 0,1,2...
or
cn 2 (n 2) (n 1) 2(n )c n ( 1)cn n 0 (7.11)
n 0,1,2,..
1 2 (1 )(5 ) 4
h( ) c0 1 ...
2! 4!
3 3 ( 3 ) (7 ) 5
c1 ...
3! 5!
c0S1( ) c1S2 ( ) (7.14)
91
Block 2 Applications of Quantum Mechanics
1 2 (1 )(5 ) 4
where S1() 1 ... and
2! 4!
3 3 (3 ) (7 ) 5
S2 ( ) .. and c0 and c1 are arbitrary
3! 5!
constants. Eq. (7.14) is the most general solution of Eq. (7.7), S1() and
S2 () are the two independent solutions.
We now calculate the ratio of the consecutive terms in the series solution
given in Eq. (7.13) , for large values of n:
c 2n 2
limn n 2 (7.16)
cn n2 n
Let us now look at the power series expansion of a different function
2
f () e :
2 2 ...
2 an 2
n n
e 1 2
2
n!
2! n 0,1,2 n 0,1,2
n
an n where an 1 2 ! (7.17)
n 0,2,4..
2
and equal to for large n. Therefore we can say that the S1() and S 2 ( )
n
2
behave as e . Therefore the series solution for ( ) is
1 1
2 2
( ) h() e 2 c0S1( ) c1S2 ( ) e 2
1 1 2
e e 2
2 2
e2
(7.19)
92
Unit 7 Simple Harmonic Oscillator-I
Clearly this solution does not satisfy the boundary condition that the wave
function goes to zero at . Clearly an infinite series solution for h( ) of
the kind in Eq. (7.14) will not give us any allowed value for the energy E. The
1
2
only way to ensure h( ) e 0 as would be if h() were a
2
polynomial and not an infinite series in . For h( ) to be a polynomial we
must have c n 2 0 for some value of n so that all consecutive coefficients
which depend on it vanish.In that case the highest power of in h( ) is n
1
1
2 En n
and ( ) n e 2 0 as . For that Eq. (7.12): 2
2n 1 0 2n 1, n 0,1,2,... (7.20)
For the values of 1, 5, 9,... , (even values of n) you can see that S1() is a
polynomial whereas S 2 ( ) is an infinite series. So for all even values of n if
you set c1 to zero you will get a polynomial solution. For the values of 7
n 3, E 3
2
3, 7,11,... , (odd values of n) S 2 ( ) is a polynomial whereas S1() is an
5
infinite series. So for all odd values of n if you set c 0 to zero you will get a n 2, E 3
2
polynomial solution. 3
n 1, E 3
2
So, for a physically wave function, the values of are discrete and the 1
n 0, E0
energy of the quantum simple harmonic oscillator is quantized: 2
1
2n 1 2 n ; n 0,1,2,...
Fig. 7.3: Energy level
2 diagram of a simple
harmonic oscillator.
1
E E n n ; n 0,1,2,... (7.21a)
2 2
(7.21b)
1
c1 c 3 3 c 5 5 .. c n n e 2
2
for n 1,3,5...
(7.21c)
SAQ 2
d 2h dh
2 2nh 0 (7.22)
d 2 d
The solutions of this equation are familiar to you, these are the Hermite
polynomials H n () with n 0,1,2,3... :
H 2 ( ) 4 2 2 21 2 2 (7.23c)
2
H 3 () 8 3 12 12 3 (7.23d)
3
4
H 4 ( ) 16 4 48 2 12 121 4 2 4 (7.23e)
3
Note that:
1 1
2 2
0 ( ) c 0 e 2 H 0 ()e 2 with c 0 1 (7.24a)
1 1
2 2
1( ) c1e 2 H1()e 2 with c1 2 (7.24b)
1 1
2 () c 0 1 2 2 e 2
2 2
H 2 ()e 2 with c 0 2 (7.24c)
1 1
2 2 2
3 () c1 3 e 2 H 3 ()e 2 with c1 12 (7.24d)
3
1 1
4 2 2
4 () c 0 1 4 2 4 e 2 H 4 ()e 2 with c 0 12
3
(7.24e)
We write the general solution for the eigenfunctions of the simple harmonic
oscillator problem as:
The following relations are also known for the Hermite polynomials:
2 n!
2 n
H n ()H n () exp( )d nn (7.26a)
And
H n 1() 2H n () 2nH n 1() (7.27)
94
Unit 7 Simple Harmonic Oscillator-I
N n is the normalization constant to be determined by the normalization
condition on the eigenfunctions: *n ( x ) n ( x )dx 1. Using Eq. (7.26a) we
can determine N n :
1
a 2
Nn (7.29)
2 n!
n
*n ( x ) n ( x ) (7.30c)
SAQ 3
a) Check the orthogonality of the wave functions:
i) 0 ( x ) and 1( x ) ii) 1( x ) and 2 ( x ) .
1/ 2
a
With n ( x ) H n (ax ) exp( a 2 x 2 / 2), n 0,1, 2,... we can write
2 n n!
down the first four eigenfunctions which are plotted in Fig. 7.4 below.
Table 7.1: Simple Harmonic Oscillator Wavefunctions
a
1/ 2
0 0 (x) exp( a 2 x 2 / 2), 2
a
1/ 2 3
1 1( x ) (2ax ) exp( a 2 x 2 / 2) 2
2
a
1/ 2 5
2 2 (x) 2a 2 x 2 1exp( a 2 x 2 / 2) 2
8
a
1/ 2 7
3
3 (x) 8a 3 x 3 12ax exp(a 2 x 2 / 2) 2
48
95
Block 2 Applications of Quantum Mechanics
a
1/ 2 9
4 4 3
4 ( x ) 2a x 6a 2 x 2 exp( a 2 x 2 2
4 6 2
1( x )
0 ( x )
ax
ax
(a)
(b)
2(x) 3 ( x )
ax ax
(c) (d)
From Eq. (7.32) we know that we can write the initial state ( t 0 ) of the
system (x,0) as:
( x,0) an n ( x ) (7.33)
n 0,1,2...
The initial state is just a linear superposition of the stationary state
eigenfunctions of the quantum oscillator . To find the coefficients an we do the
following:
n* ( x ) ( x,0) dx ak *n ( x ) k ( x ) dx
k 0,1,2...
ak nk an (7.34)
k 0,1,2...
Therefore : an *n ( x ) ( x,0) dx .
The probability density of finding the the oscillator in the state n (x ) at t 0
is a n 2 . The probability density of finding oscillator in the state n (x ) at a
97
Block 2 Applications of Quantum Mechanics
2
later time t is also an . If the initial state of the system is normalized, we
have
* ( x,0) ( x,0) dx 1 an 1
2
(7.35)
n 0,1,2...
iEn t iE t
k
Then * ( x, t ) ( x, t ) dx
an* *n ( x )e ak k ( x )e dx
k 0,1,2...
n 0,1,2...
i En En t
*
an a k e
*n ( x ) k ( x ) dx
n 0,1,2... k 0,1,2...
i En En t
an* ak e nk
n 0,1,2... k 0,1,2...
an 2 (7.36)
n 0,1,2...
SAQ 4
The initial wave function for a simple harmonic oscillator is
1 2
( x,0) 1( x ) i 2( x )
5 5
where 1, 2 ,..., are the normalized eigenfunctions of the simple harmonic
oscillator.
i) Show that * ( x,0) ( x,0) dx 1
ii) Determine ( x, t )
iii) Determine the expectation value of Ĥ in the state (x,0) .
98
Unit 7 Simple Harmonic Oscillator-I
The answer lies in considering not one single eigenfunction but a
superposition of eigenfunctions as in a wave packet. Consider for example,
the following superposition ( x, t ) of the first two oscillator eigenfunctions:
1
( x, t ) exp( iE 0 t / ) 0 ( x ) exp( iE1t / )1( x ) (7.38a)
2
And * ( x, t )
1
exp(iE0t / ) 0* ( x ) exp(iE1t / )1* ( x ) (7.38b)
2
So ( x, t ) 2 * ( x, t )( x, t )
1 *
2
0 0 1* 1 0* 1 exp( it ) 1* 0 exp(it )
1
0 2 12 2 0 1 cos t
2
(7.39)
1
Notice that ( x, t 0) 2 0 2 12 2 0 1
2
And ( x, t
2 2 1
) 0 2 12 2 0 1
2
2 2
Therefore ( x, t 0) 2 ( x, t ) . Clearly, the probability density
oscillates with time with just the frequency of the harmonic oscillator, as
2
expected classically. If we plot ( x, t ) , we get Fig. 7.5, where the plot is
made for four different values of time. It is therefore reasonable to except that
when we take a superposition of a large number of oscillator eigenfunctions
we will get a classical behaviours.
2 2
( x, t ) ( x, t )
ax ax
2 2
( x, t ) ( x, t )
ax ax
Fig. 7.5: The probability corresponding to the superposition of the first two
oscillator eigenfunctions of equal amplitude of Eq. (7.39) (with their
time dependence included) plotted at four different times a) t 0 ;
99
b) t / 2 ; c) t ; and d) t 3 / 2 .
Block 2 Applications of Quantum Mechanics
You should be very clear, that the quantum solution of the harmonic oscillator
is radically different from that the classical oscillator. In classical mechanics,
the oscillator is forbidden to go beyond the potential, beyond the turning points
where its kinetic energy turns negative. But clearly, the quantum wave
functions extend beyond the potential, and thus there is a finite probability for
the oscillator to be found in a classically forbidden region.
SAQ 5
a) Determine the classical turning points of a simple harmonic oscillator with
1
an energy given by E n n .
2
b) Show that the probability distribution of a particle in a harmonic oscillator
2
potential returns to its original shape after the classical period T for
any general harmonic oscillator state.
As an example, let us compare the quantum and classical probabilities for the
states corresponding to n = 0 , n = 1 and n = 2. The quantum probabilities are
easily calculated by taking the square of the appropriate wave functions, 0 ,
1 and 2 .
The expression for the probability of finding a classical harmonic oscillator of
mass m and energy E, governed by the equation x A sin t in a region x
is given as
1 1
P ( x ) x x (7.40)
2A (1 x / A 2 )1 / 2
2
P1( x )
P0 ( x )
2
P2 ( x ) 0 (x )
2 2
2 (x ) 1(x )
We can determine the classical amplitude corresponding the nth eigen state by
100 equating the maximum energy of the classical oscillator to its energy
Unit 7 Simple Harmonic Oscillator-I
1 2 1
eigenvalue in that state so m 2 An E n n and derive the
2 2
corresponding classical probability for the nth eigen state Pn (x ) by replacing
A by An in Eq. (7.40).
The quantum and classical probabilities are compared in Fig. 7.6 for n = 0,
n = 1 and n = 2, respectively. In both cases, the quantum probability does not
vanish in the classically forbidden region. For n = 1, the classical probability is
maximum at the turning points. But the quantum probability reaches the
maximum much closer to the point of equilibrium. For large n, the average of
the quantum mechanical probability distribution is given by the classical
probability curve.
Let us now consider an application of the simple harmonic oscillator to a
physical system: the vibrations of the two atoms of a diatomic molecule.
7.2.7 Examples of Simple Harmonic Oscillator Systems
Diatomic Molecule R1 R2
The simple harmonic oscillator serves as an important model for the
vibrational motion in a diatomic molecule. Let us assume that in a particular A c.m B
diatomic molecule, both the atoms in the molecule execute simple harmonic
Fig. 7.7: Vibration of
motion about their equilibrium positions. Hence, they satisfy the following two atoms A and B in a
equations diatomic molecule.
d 2R1
M1 k (R R e ) (7.41a)
dt 2
and
d 2R2
M2 k (R Re ) (7.41b)
dt 2
where R1 and R2 are the distance of the two atoms A and B from their centre
of mass and R R1 R 2 (Fig. 7.7). The masses of the two atoms are M1 and
M 2 k is the force constant and at equilibrium, the distance between the two
atoms is Re . Considering the moment about A (see Fig. 7.7) we obtain
M 2R (M1 M 2 )R 1 (7.42)
Putting Eq. (8.42) in Eq. (8.41a) we obtain
M1M2 d 2R
k (R Re ) (7.43)
M1 M2 dt 2
or
d 2x
k x (7.44)
dt 2
M1M 2
with x R Re and .
M1 M 2
Thus we have reduced a two body problem of masses M1 and M 2 to a one-
body problem of mass and the whole molecule behaves as a simple
harmonic oscillator of mass (reduced mass of the molecule) having force
constant k. Hence the eigenfunctions and eigenvalues of the molecules are
given by Eq. (7.30a) and Eq. (7.30b), respectively. These equations have
been very useful in understanding the vibrational spectrum (obtained in the
near infrared region of the electromagnetic waves) of diatomic molecules. The 101
Block 2 Applications of Quantum Mechanics
analysis of the experimental spectrum has yielded force constants of a large
number of heteronuclear molecules.
The quantum oscillator has implications even beyond the simple diatomic
molecule. It is the foundation for the understanding of complex modes of
vibration in larger molecules, for example polyatomic molecules can also be
modelled by coupled harmonic oscillators. The atoms in large molecules are
treated as point masses and the bonds connecting then act (approximately)
like springs, the motion of atoms in a solid lattice, the theory of heat capacity,
etc. Let us consider a simple example of such a coupled system.
Coupled spring-mass system
Consider the system shown in Fig. 7.8 where two blocks of mass m are
k
connected by springs of spring constant k . The displacement of the
m
two masses are x A and x B respectively.
p 2 p 2 1
H A B m2 x A 2 x B 2 ( x A x B ) 2
2m 2m 2
(7.45)
x xA x xB
m m
x
x 0
SAQ 6
a) Consider a proton as a bound oscillator with a natural frequency of
3 10 21 Hz. Calculate the energy of its ground state and first excited state.
b) Calculate x and p x for the ground state harmonic oscillator
eigenfunction.
102
Unit 7 Simple Harmonic Oscillator-I
There is another method of solving the simple harmonic oscillator problem in
quantum mechanics. This method is sometimes called the algebraic method,
the method explained in Sec. 7.3 is also called the analytic method. We now
discuss the algebraic method in brief.
pˆ 2 1
Hˆ m2 xˆ 2 pˆ (mxˆ )2
1 2
(7.48)
2m 2 2m
Notice that the operators â and â are the adjoints of each other. Now
1
aˆ aˆ † (ipˆ mxˆ ) ( ipˆ mxˆ )
2m
1
pˆ 2 (mxˆ )2 impˆ xˆ xˆpˆ
2m
1
pˆ 2 (mxˆ )2 imxˆ, pˆ (7.52)
2m
Using xˆ, pˆ i in Eq. (7.52), we get:
aˆ aˆ †
1
2m
pˆ 2 (mxˆ )2 m
1 pˆ 2 1 1 1
m2 xˆ 2 (7.53)
2m 2 2
So the stationary state Schrödinger equation (Eq. 7.49) for the simple
harmonic oscillator reduces to
1
aˆ † aˆ ( x ) E( x ) (7.55)
2
You can verify for yourself that the commutator of â and â is:
SAQ 7
Show that [aˆ, aˆ ] 1 .
Hˆ (aˆ † ) E aˆ † (7.60)
1 1
Hˆ (aˆ ) aˆ † aˆ (aˆ ) aˆ † aˆ aˆ aˆ (7.61)
2 2
Clearly â is a stationary state of the Hamiltonian with an eigen energy less
than that of the stationary state by .
Eqs. (7.60) and (7.64) therefore show that given any stationary state , we
can generate eigen states of the Hamiltonian with higher or lower energies by
operating on by the operators ↠or â respectively.
104
Unit 7 Simple Harmonic Oscillator-I
â and ↠are called the ladder operators, because they help us climb down
or climb up to energy states with lower or higher energies.
Does this then mean that using the operator â on any stationary state, ,
repeatedly, we can find energy eigen states with lower and lower energies,
even with energy less than zero? That is not the case, because we know that
the eigen energy of the simple harmonic oscillator must be positive definite.
Therefore, there must be a state, which we can denote as the lowest energy
state or ground state 0 ( x ) , for which
aˆ 0 ( x ) 0 (7.65)
We use Eq. (7.65) and Eq. (7.51a) to write the following differential equation
for the ground state eigenfunction:
1 d mx ( x ) 0 d 0 m x (7.66)
0 0
2m dx dx
Eq. (7.66) can be solved to get:
m
x2
0 ( x ) N 0 e 2 (7.67)
SAQ 8
Use Eq. (7.72) to obtain 1( x ) . Is the wave function normalized?
7.4 SUMMARY
The simple harmonic oscillator potential is important in physics
because in the neighbourhood of a local minimum (say at x = a),
almost any arbitrary potential function V (x ) can be approximated by
a parabolic potential
1 d 2V
V ( x ) k ( x a ) 2 where k
2 dx 2 x a
the values of are found to be discrete and hence the energy of the
quantum simple harmonic oscillator is quantized and:
1
energy eigen values are E n n ; n 0,1,2,...
2
where an *n ( x ) ( x,0) dx , (x,0) being the wave function of the
system at t = 0.
The energy eigenvalues and eigenfunctions of a simple harmonic
oscillator can be determined using ladder operators â and ↠which
are defined as follows:
1
aˆ ( mxˆ ipˆ ) ;
2m
1
aˆ † (mxˆ ipˆ )
2m
â and â are called the ladder operators, because they help us climb
down or climb up to energy states with lower or higher energies
respectively:
n ( x ) Nn (aˆ † )n 0 ( x )
Where 0 ( x ) is the ground state eigenfunction.
107
Block 2 Applications of Quantum Mechanics
9. The initial state of the simple harmonic oscillator of mass m and frequency
is:
( x,0)
1
3
0 ( x ) i
2 1( x )
So Eq. (7.3) is
2 a 2 d 2 1 m 2 2
E ( ) (i)
2m d 2 2 a 2
2m
Multiplying Eq. (i) by we get:
2a 2
d 2 ( ) m 2 2 2 2m
( ) E ( )
d 2 2a 2 2a 2
d 2 ( ) m 2 2 2 2m
( ) E ( )
d 2 2
a 4 2a 2
m m 22
Since a 2 a4 we get:
2
d 2 ( ) 2E
2 ( ) ( )
d 2
d 2 ( ) 2E
Or 2 () 0 with
d 2
1
1 2 (1 )(5 ) 4 2
n ( ) c 0 1 e 2 for n 0,2,4
2! 4!
1
3 3 2
c1 e 2 for n 1,3
3!
2n 1 1 n ( )
n En n
2
0 1 1
2
2 0 ( ) c 0 e 2
1 3 3 1
2
2 1() c1e 2
109
Block 2 Applications of Quantum Mechanics
2 5 5 1
2 () c 0 1 2 2 e 2
2
2
3 7 7 4 2
1
2 3 () c1 3 e 2
3!
1
2 2
c1 3 e 2
3
4 9 9 8 32 4 2
1
2 4 ( ) c0 1 2 e 2
2! 4!
1
4 2
c0 1 4 2 4 e 2
3
a
2axe a x dx 0 , since the integral is
2 2
3. a) i) 0 ( x ) 1( x ) dx
To evaluate the
2
integrals in this unit,
odd.
you may Table 3.1 of
Unit 3 , Block 1.
a 2 2
ii) 1( x ) 2 ( x ) dx [2ax(4a
2 2
x 2) ]e a x dx
4
8a 3 x 3 4ax e a x
a 2 2
dx 0
4
e a x
2 2
N 02 02 ( x ) dx 1 N 02 dx 1
N02 1
a2
1 1
a 2 m 4
N0
ii) The normalization condition is
4a 2 x 2e a x
2 2
N12 12 ( x )dx 1 N12 dx 1
2 a 2 x 2 1 2 2
4a 2N12 x e dx 1 4a 2 N12 1 N1 1
2 a6 a
1 1
a 2 m 4
N1
2 4
1 2
4. i) * ( x,0) 1* ( x ) i *2 ( x )
5 5
1 * 2 * 1 2
And * ( x,0)( x,0) 1( x ) i 2 ( x ) 1( x ) i 2 ( x )
5 5 5 5
110
Unit 7 Simple Harmonic Oscillator-I
1 4
* ( x,0) ( x,0) dx 5 1* 1 i 2 5 *2 2 dx
1 4
5 1* 1 dx
5 *2 2 dx 1
ii) Since 1, 2 are normalized eigenfunctions, 1* 1 dx *2 2 dx 1
1 2
Hˆ ( x,0) Hˆ 1( x ) i 2 ( x )
5 5
3 5
You know that: Hˆ 1 E1 1 1 ; Hˆ 2 E 2 2 2
2 2
1 3 2 5
So Hˆ 1( x ) i 2 ( x )
5 2 5 2
1 * 2 * 1 3 2 5
Hˆ 5
1 i
5
2
5
1 i
2 5
2 dx
2
1 3 4 5
5 2
1* 1 dx *2 2 dx
5 2
25 * 23 * 23
52
i 1 2 dx i 21 dx .
52 10
The integrand is an odd function. Hence the integral over the interval
will be zero.
x 0
Similarly, p x i 0* ( x ) x 0 ( x ) dx
a a2x 2 a2x 2
i
exp
2
( a 2 x ) exp
2
dx
a3
i
x exp ( a 2 x 2 ) dx
1 1
7. [aˆ, aˆ † ] (mxˆ ipˆ ), (mxˆ ipˆ )
2m 2m
1
m 2 2 xˆ, xˆ pˆ, pˆ impˆ, xˆ imxˆ, pˆ
2m
1
im i imi 1
2m
since xˆ, xˆ pˆ, pˆ 0 and xˆ, pˆ i.
1/ 4 mx 2
8. 1( x ) N1(aˆ † ) 0 ( x )
N1 d mx m e 2 (i)
2m dx
m m
d e 2 x mxe 2 x
2 2
and (ii)
dx
Therefore Eq. (i) reduces to
1 / 4 mx mx 2
2
1/ 4
N1 m m 2m
1( x ) 2mx e 2 xe 2
2m
To determine N1 we must calculate 1* ( x ) 1( x ) dx :
m 2
m 2m x
1* ( x ) 1( x ) dx N1 2
x 2e dx 1 N1 1
Terminal Questions
1. m 10 12 kg; 2 6.28 10 4 s 1 ; Amplitude A 10 3 m
1 1
m2 A 2 10 12 6.28 10 4 10 3 19.7 10 10 J
2 2
E
2 2
(i)
E n n n 6.054 10 34 6.28 10 4
1 1
2 2
38.01 10 30 n
1
2
(ii)
n .5 10 20
1
ii) The zero point energy 19.0 10 30 J
2
1
iii) We have m2 A2 19.0 10 30 J
2
38.0 10 30
A2 1034 m2
10 12 6.28 10
4 2
or A 10 17 m .
113
Block 2 Applications of Quantum Mechanics
2. x ( n , x n ) n* ( x ) n ( x ) dx
Since n (x ) is of definite parity, it is either an odd or an even function of x.
in either case, the product n* ( x ) n ( x ) will be even. Since x is odd, the
integrand will be an odd function of x and hence the integral will be zero.
3. The expectation value of x̂ 2 in the ground state is
a a 1 1
xˆ 2 x 2e a x
* 2
0 ( x ) x 0 ( x ) dx
2 2
dx
2 a 6 2a 2
xˆ 2
2m
d 2 0
pˆ x 2 0* ( x ) p x2 0 ( x ) dx and pˆ x2 0 ( x ) 2
dx 2
1/ 2 a2x 2
d 0 a
2 2
(a x ) e
dx
1/ 2
d 2
2
a
a2
d a 2 x 2 2
xe
dx
a5 / 2
1 / 2
e a x / 2 a 2 x 2e a x / 2
2 2 2 2
dx ( )
e a x
2a 3 1 2 2 1
a 2 x 2 e a x dx
2 2 2 2
pˆ x2 a m
2 2
Using the results of TQ3 0* ( x ) x 2 0 ( x ) dx we get
2m
k m2 1
V .
2 2m 2 2m 4
1
Since the ground state eigen energy is E0
2
1 1
K .E. E 0 .
4 4
pˆ 2
pˆ x 2
(You can also evaluate K .E. 0* ( x ) x 0 ( x ) dx ).
2m 2m
5. The potential function is identical to the SHO potential for x > 0. However
since V (x ) for x 0, the wave function must satisfy the condition:
( x 0) 0 (as in a rigid box), the only solutions that are acceptable are
those for which ( x 0) 0 .
(iii)
Setting the coefficient of x 4 0 in Eq. (iii) we get
2 2 2 m2 m 2 2 m
2 (iv)
m 2 4 2 2
Substituting for in Eq. (iii) we get
d 2 1 2
2 5
2 m2 x 2 e x x 2
2 2 2
dx m 2
5 x 2 2 1 2
e x 5 m
2
1 2 2 m
Setting 1, we get
5 m 5
2m x 2 1
5
2 d 2 1 5
And m2 x 2
2m dx 2 2 2
5
E
2
7. Using the results of SAQ 2b and TQ 2
2 m
x xˆ 2 xˆ 2 ; p x pˆ x 2 pˆ x
2m 2
m
x p x /2
2m 2
8. Using Eq. (7.72) and 1( x ) from SAQ 8
1 mx 2
† N2 d m 4 2m 2
2 ( x ) N2 a 1( x ) m x xe
2 m dx
115
Block 2 Applications of Quantum Mechanics
1 1
mx 2 mx 2
N2 m 4
2m 2 d xe 2 mx 2 e 2
2m dx
1
mx 2 mx 2
m 4 m 2
N2 2 x e 2 e 2
1 a2 x 2
m 4
2a 2 x 2 1e
a 2 2 / 2
N 2 2 N2 2 2 1 e
22
it i 3t
1 2 2
( x, t ) 2
e 0(x) i e ( x )
3 3
it i 3t
1 2
* ( x, t ) e 2 0 ( x ) i e 2
3 3
( x, t ) 2
1
3
2
0 ( x ) 2 1( x ) 2
3
i 2 i t
3
e
e it 0 1
1 2 2 2 2
2 sin t 0 1
3 0 3 1 3
1 2 2 2 2
0 1 2 0 1 sin t
3 3 3
2
2 1 2 2 1 2 2 2
at t 0 ( x,0) 02 12 x, t 0 1
3 3 3 3
ii) xˆ * ( x, t ) x ( x, t ) dx
1
2 ( x ) dx 2 x 2 ( x ) dx
x
3 0 3 1
2 it 2 it
i
3
e x 0 ( x ) 1( x ) dx i 3
e x 0 ( x ) 1( x ) dx
i
3
2 it
e e it x0 ( x ) 1( x ) dx
2
2 sin t x 0 ( x ) 1( x ) dx
3
So x x 0 sin t
116
Unit 7 Simple Harmonic Oscillator-I
2 2
where x0
3 x 0 ( x ) 1( x ) dx
1
4a 2 2 a 2 x 2 4a 2 1 2 2 2
x e dx .
3a 3 m
3 3 2 a6
2 2 2 2 2 2
2m 2 2m 2 2m 2 2 m x y z ( x, y , z ) E( x, y , z )
1 2 2 2 2
x y z
2 d 2 x 1 2 d 2 y 1
m2 x 2 x y z m2 y 2 y x z
2
2m dx 2 2 2m dy 2
2 d 2 y 1
m 2 z 2 z x y E x y z
2m dz 2 2
2 d 2 x 1
m2 x 2 x E x x
2m dx 2 2
2 d 2 y 1
m2 y 2 y E y y
2m dy 2 2
2 d 2 z 1
m2 z 2 z E z z
2m dz 2 2
Using the results for the eigen energies of the simple harmonic oscillator,
we can write
1 1 1
E x n x ; E y n y ; E z n z
2 2 2
Where n x , n y , n z 0,1,2,3....
So that
3
E E x E y E z n x ny nz
2
117
Block 2 Applications of Quantum Mechanics
k 1860 Nm 1 1860
11. 2 s2
6.85 amu 27
6.85 1.66 10
40.5 1013 s 1
1 1
E 6.054 10 34 40.5 1013 J .1330 eV
2 2
3
E1 .4 eV E1 E0 0.27 eV
2
118
Unit 8 Spherically Symmetric Potentials
UNIT 8
SPHERICALLY SYMMETRIC
POTENTIALS
Structure
8.1 Introduction 8.3 Space Quantization
Expected Learning Outcomes 8.4 Radial Eigenfunctions
8.2 Three Dimensional Schrödinger 8.5 Summary
Equation for a Central Potential 8.6 Terminal Questions
Schrödinger Equation in Spherical 8.7 Solutions and Answers
Polar Coordinates
Eigenfunction and Eigenvalues of
L̂z Spherical Harmonics
Parity of the Spherical Harmonics
8.1 INTRODUCTION
In the previous three units you have obtained the eigenfunctions and
eigenvalues of a number of one-dimensional systems. In this unit, we shall
extend our study to a three-dimensional system. Thus now there will be three-
independent variables, which can be x, y, and z, in the Cartesian coordinates
system or r , and in the spherical polar coordinate system. Hence, the
number of degrees of freedom of the particle will increase from one to three
and the time independent Schrödinger equation will now be a three-
dimensional differential equation.
In general, the potential in which a particle moves in a three-dimensional
space is a function of all three coordinates. However, in the present unit we
shall confine ourselves to those potentials which depend only upon the radial
coordinate r and are independent of the polar coordinates and . Such
potentials are known as spherically symmetric potentials and the
corresponding physical systems are called spherically symmetric systems.
1
The isotropic harmonic oscillator potential of TQ 9, Unit 7 V (r ) m2 r 2 is
2
an example of a spherically symmetric potential. Another example would be a
particle moving freeing in a spherical box of radius R0 :
0 r R0
V (r )
r R0
2 2
2 V (r ) (r ) E(r ) (8.1)
where E is the total energy of the particle, V (r ) is its potential energy and
(r ) (r , , ) is the wave function of the particle ,that depends on all three of
its coordinates. Note that V (r ) is independent of the polar angles and . The
force F acting on such a particle will be directed along r F V . So
classically, the torque on the particle is equal to r F . Since F and r are
in the same direction, is equal to zero. Furthermore, the torque is equal to
the rate of change of the angular momentum L . Hence, the angular
momentum of a particle moving under a spherically symmetric potential (which
120
Unit 8 Spherically Symmetric Potentials
is also known as a central potential) will not change with time, it is constant in
magnitude and direction and is a constant of motion for the object. In your
mechanics undergraduate courses you have studied that the angular
momentum is a constant of motion for all central force motion. Recall that you
used this property to obtain Keplerian orbits for planetary motion around the
sun.
However, a constant L means that all its three components Lx , Ly , and Lz are
constant simultaneously. This is not possible in quantum mechanics because
the three components of the angular momentum operator L̂ , Lˆx , Lˆy , and L̂z do
not commute among themselves (see Unit 4). Thus, there is a difference
between the classical and quantum interpretations of angular momentum.
Instead of relating angular momentum to torque (as in classical mechanics), in
quantum mechanics we find that the Hamiltonian can be written in such a way
that it depends only on the angular momentum. This in how angular
momentum makes its entry into the scheme of quantum mechanics.
We now write down the Schrödinger equation in spherical polar coordinates.
8.2.1 Schrödinger Equation in Spherical Polar Coordinates
In spherical polar coordinates, 2 is given by
1 2 1 1 2
2 r sin (8.2a)
r 2 r r r 2 sin r 2 sin 2 2
Putting this expression for 2 in Eq. (8.1) and writing (r ) (r , , ) we get
r 2 2 (E V (r )) r 2
r r 2
1 1 2
(sin ) (8.2b)
sin sin2 2
Eq. (8.2b) suggests that (r , , )) can be separated in the variables r , and
as follows:
(r , , ) R (r ) Y (, ) (8.3a)
The normalization condition for * (r ) is a volume integral over the
coordinates r , ,
2
3 2
* (r )(r )d r * (r , , )(r , , )r sin drdd 1
r 0 0 0
(8.3b)
which is
2
R * (r )R (r )r 2 dr
0
Y * ( , )Y (, ) sin dd 1
0 0
(8.3c)
Putting Eq. (8.3) in Eq. (8.2) and using the method of separation of variables
we get the following two equations
121
Block 2 Applications of Quantum Mechanics
1 2 R (r ) 2 K
r 2 (E V (r )) 2 R (r ) 0 (8.4)
2 2
r r r r
and
1 Y (, ) 1 2Y (, )
sin K Y (, ) (8.5)
sin sin2 2
where K is a constant. We can further show that the operators L̂2 and L̂z in
spherical polar coordinates are given by
1 1 2
Lˆ2 2 sin (8.6a)
sin sin 2 2
Lˆz (8.6b)
i
In fact, you can like to do this exercise yourself. Try the following SAQ.
SAQ 1
r 2 2 (E V (r )) r 2 Lˆ2 (8.7a)
r
r 2 2
You have established in SAQ 1 that L̂2 commutes with the Hamiltonian, so
Lˆ2 , Hˆ 0 (8.8a)
Recall Eq. (4.59) of Unit 4 which tells us that for any operator D̂ , if Dˆ , Hˆ 0 ,
d Dˆ
then 0, i.e., D̂ is constant. Applying this result to Dˆ Lˆ2 we get
dt
L̂2 constant (8.8b)
Substituting Eq. (8.9a) and Eq. (8.6a) in Eq. (8.7b), and using the method of
122 separation of variables, we get
Unit 8 Spherically Symmetric Potentials
sin d dP ( ) 2 1 d 2
P () d sin d K sin d 2 (8.9b)
Eq. (8.9b) shows that both sides are equal to the same constant. Let us
denote this constant by ml2 . So we get
1 d 2
ml2 (8.10)
d 2
and its solution is
() Ae iml (8.11)
Where A is a constant. Now () also has to be single valued for all , hence
we must have
() ( 2) or Ae iml Ae iml ( 2) (8.12)
angles 0 and 2 are actually the same. So: Ae ( 2iml ) 1 and therefore
ml has to be an integer:
ml 0,1,2,....... (8.13)
To determine the constant A , we apply the normalization condition
2
* ( ) ( ) d 1 (8.14)
0
or
2
iml 1
e iml d 1 A
2
A e 2
(8.15)
0
1
So finally: ml () e iml (8.16a)
2
Notice that we have labelled the function () by the index ml where the
allowed values of ml are given by Eq. (8.13). You can check that when the
operator L̂z (Eq. 8.6b) operates upon ml () (Eq. 8.16a) we get
SAQ 2
Derive Eq. (8.18) from Eq. (8.17).
All that we know about Eq. (8.18) is that ml is an integer. To determine the
function P (v ) , we take two particular cases.
Case I: ml 0
d 2 dP (v )
dv (1 v ) dv KP (v ) 0 (8.19a)
d 2P (v ) dP (v )
or (1 v 2 ) 2v KP (v ) 0 (8.19b)
2 dv
dv
Notice that this equation has regular singularities at v 1 but is analytic at
v 0 . Therefore in the range 1 v 1 ( 0 ) , we can choose a power
series solution to this equation of the form
P (v ) ck v k (8.20a)
k 0,1,2,...
dP d 2P
So
c k k v k 1;
dv k 0,1,2..
dv 2 k 0,1,2..
c k k (k 1) v k 2 (8.20b)
Substituting from Eq. (8.20a and b) into Eq. (8.19a) and collecting the
coefficients of v k we get the relation between the coefficients as:
k ( k 1) K
ck 2 ck (8.20c)
(k 2) (k 1)
and
K K 2 K 2 K 6
c2
c0 ; c3 c1; c 3 c1; c 4 c0
2 6 6 12
(8.20d)
The general solution is
P (v ) c 0 S1 (v ) c1S 2 (v ) (8.21)
1 K
1(1 )
c k k 1
limk k 2 lim 1 (8.22a)
ck 0 2 1
k (1 ) (1 )
k k
And P (v ) c0 1 v v 2 .. . c0
1
1 v
(8.22b)
124
Unit 8 Spherically Symmetric Potentials
The series in Eq. (8.22b) diverges at v 1. The only one can get a physically
acceptable solution for P (v ) is if the series were to terminate at some
value of k, i.e. c k 2 0 for at some value of k. So
k (k 1) K
ck 2 c k 0 K k (k 1) (8.22c)
(k 2) (k 1)
where k 0,1,2,... . Suppose we write K l (l 1) , the series terminates when
l (l 1) k (k 1) for some integer value of k 0 . We can just pick l k to
get the allowed values of l to be 0,1,2.... Thus the values of K are quantized,
just like the values of ml .
even ( l 0,2,4,... ) then the even series S1 (v ) will terminate with the highest
odd ( l 1,3,4,... ) then the odd series S2 (v ) will terminate with the highest
value of v in S2 (v ) being v l but the even series, S1 (v ) will still be an infinite
series. Therefore for odd values of l we must have c 0 0 .
The resulting solutions for different values of k are called the Legendre
polynomials. We can label the Legendre polynomial of order l by Pl (v ) and
it is a polynomial of degree k. You have studied about Legendre polynomials
in Unit 4 of MPH-001.The first few Legendre polynomials are
l 0 P0 (v ) 1 (8.23a)
l 1 P1(v ) v (8.23b)
l 2 P2 (v )
1
3v 2 1 (8.23c)
2
l 3 P3 (v )
1
5v 3 3v (8.23d)
2
You have already studied the properties of Legendre polynomials in Unit 4 of
MPH-001 and you know that:
1
2
Pl (v )Pl (v )dv 2l 1 ll (8.24)
1
P (v ) 1 v 2
ml / 2
g (v ) (8.27)
Differentiating once with respect to v we get:
ml
dP (v ) d 1 v 2 2 g (v )
dv dv
(8.28a)
ml ml
dg (v ) 1
1 v 2 2 ml v 1 v 2 2 g (v )
dv
d
ml ml
d 2 dP (v ) 2 2 1 dg (v ) 2 2
And 1 v 1 v m v 1 v g (v ) (8.28c)
dv dv
l
dv dv
ml 2 ml
2 2 1 d g dg
1 v 2ml 1v 1 v 2 2
2 dv
dv
ml
1
ml ml 1v 2 1 1 v 2 2 g (v ) (8.28d)
Substituting from Eq. (8.28d) into Eq. (8.18) we get:
ml m m
1 v
2 l l
2 2 1 d g dg 1
2ml 1v 1 v 2 2 ml ml 1v 2 1 1 v 2 2 g (v )
2 dv
dv
ml
ml2
K 1 v 2 2 g (v ) 0 (8.29a)
(1 v 2 )
ml
Multiplying Eq. (8.29a) by 1 v 2 2 we finally get:
(1 v 2 )
d 2g
dv 2
2(ml 1)v
dg
dv
K ml (ml 1) g 0 (8.29b)
126
Unit 8 Spherically Symmetric Potentials
Now when ml 0 , Eq. (8.29b) is just Eq. 8.19b ( with g (v ) Pl (v ) ) and the
K m l 1 ( m l 2)
d 2g
dv 2
0 (8.30)
dg
This is the same equation with g (v ) and ml ml 1 . So if Pl (v ) is a
gv
dPl (v )
solution of Eq. (8.29b) with ml 0 , then is a solution of Eq. 8.30 or
dv
d 2Pl (v )
Eq. 8.29 with ml 1 . In the same way is a solution of Eq. (8.29b) with
dv 2
ml 2 and so on. In general, therefore the function:
d ml
Plml (v ) 1 v 2
ml / 2
Pl (v ) (8.31)
dv ml
is a solution of Eq. (8.18) for arbitrary ml .
The functions defined in Eq. (8.31) are called the associated Legendre
functions Plml (v ) which are obtained by differentiating the Legendre
So far we have only considered only values of ml 0 . Notice that Eq. (8.18)
contains only ml2 and not ml , so the ODE is invariant under the
transformation m l m l . So the solutions for ml are proportional to each
other and it can be shown that:
ml (l ml )! ml
Pl (v ) 1ml Pl (v ) (8.32)
( l ml )!
ml
where Pl (v ) is:
d ml
(v ) 1 v 2
ml ml / 2
Pl Pl (v ) (8.33)
dv ml
with v cos and ml l . So we have
l ml l (8.34a)
Alternatively Eq. (8.33) can also be written as ( with v cos ) :
ml d ml
Pl (cos ) sin ml Pl (cos ) (8.34b) 127
dv ml
Block 2 Applications of Quantum Mechanics
Quantum mechanically acceptable solutions of Eq. (8.7) with K equal to
l (l 1) are obtained when the l is equal to one of the integers
l 0,1, 2,..... (8.34c)
And for a given integer l there will be following (2l 1) values of ml :
l , l 1, l 2,...,0,..., l 1, l (8.35)
SAQ 3
a) Use the Legendre polynomial P1 ( x ) x and Eq. (8.34b) to construct
P10 ( x ) and P11( x ) .
b) Use Eqs. (8.36 and 8.37) to construct Y1,0 (, ) , Y1,1 (, ) and Y1,1 (, ) .
1 1 / 2
Y00 (8.40a)
4
1/ 2
3
Y10 cos (8.40b)
128 4
Unit 8 Spherically Symmetric Potentials
3 1/ 2
Y1,1 sin e i (8.40c)
8
5 1 / 2
Y20 (3 cos 2 1) (8.40d)
16
1/ 2
15
Y2,1 sin cos e i (8.40e)
8
15 1 / 2
and Y2,2 sin 2 e i 2 (8.40f)
32
The squares of some of these functions (which also represent the angular part
of the wave function of the hydrogen atom) are shown in Fig. 8.1. You may
now like to perform an exercise based on the ideas discussed so far.
2 2 2 2
Fig 8.1: Polar plots of Yl ,ml ( , ) (a) Y0 ,0 ( , ) (b) Y1,0 (, ) (c) Y1,1 ( , )
2 2 2
(d) Y2 ,0 ( , ) (e) Y2 ,1 ( , ) and (f) Y2 ,2 ( , ) .
SAQ 4
a) Show that Yl ,ml (, ) is an eigen function of Lz . Determine its
eigenvalues.
b) Show that Y2,2 is normalised and is orthogonal to Y2,2 .
129
Block 2 Applications of Quantum Mechanics
ml d ml
Yl ,ml (, ) Constant Pl ml (cos ) e iml with Pl cos sin ml
dv ml
Pl (cos ) . Now
Therefore, the parity of Yl ,ml ( , ) depends only on the value of l and is given
SAQ 5
Use the expression given by Eq. (8.40e) for Y2,1(, ) and verify that it is of
even parity.
To sum up, so far we have obtained the solutions of the angular part of the
stationary states of a particle moving in a spherically symmetric potential.
These are nothing but the eigenfunctions of the angular momentum operator
L2 . Their exact functional dependence on and is given by spherical
harmonics. The eigenvalues of the operator L2 are l (l 1) 2 where l takes
discrete integral values.
Let us now try to understand what these results mean physically, in terms of
what is called space quantization.
130
Unit 8 Spherically Symmetric Potentials
quantum mechanical angular momentum as compared with its classical
counterpart.
Classically, for the same magnitude of the angular momentum, we can obtain
an infinite number of states by changing the direction of the agular momentum
vector. But quantum mechanically, for each value of angular momentum, there
are only a finite number of states characterised by l and ml . Moreover, in
quantum mechanics, the components of L̂ in two of the three directions being
uncertain, we do not describe a state by specifying the directions of the
angular momentum vector. Instead, we give the component of the angular
momentum along a specific direction. We conveniently choose this direction to
be along the z-axis. So how do we visualise this situation?
There is a useful pictorial way to communicate these quantum mechanical
results – this the so called vector model of the angular momentum. In this
model we represent the angular momentum of the particle in motion is given
by a vector L of length [l (l 1)]1/ 2 . The angular momentum vector precesses
around the z-axis in such a way that the magnitude of L (hence L2 ) and
Lz (projection of L on z-axis) are constants (see Fig. 8.2a).
z
ml 2
6
ml 1
ml 0
Lz
L
ml 1
ml 2
(b)
(a)
Fig.8.2: a) Precession of L about z-axis; b) space quantization for l 2 . The
radius of the circle is [ 2( 2 1)]1 / 2 6 . The multiplicity of states is 5.
Since for a given value of l , the eigenvalues of L̂z are ml with integer values
of ml (ranging from l to l ) , the component of L along the z-axis is
quantized. A measurement of Lz will yield only the 2l 1 quantized values,
with a maximum value l less than the magnitude of the vector L for l 0 .
Further, the vector L can
make only certain quantized angles with the z-axis;
the angle , between L and Lz can take only discrete values given by
ml
cos (8.43)
[l (l 1)]1 / 2
This phenomenon of the quantization of the direction of L with respect to one
of the coordinate axes, is known as space quantization. Since ml is always
less than l (l 1) (except for l 0) , the vector L can never be along z-axis. For
l 2, the values of ml are 2, 1, 0, –1 and – 2 as shown in Fig. 8.2b.
131
Block 2 Applications of Quantum Mechanics
Furthermore, although L̂x and L̂y are uncertain, Lˆ2x Lˆ2y being equal to Lˆ2 Lˆ2z
have definite non-zero values unless l 0; however, the values of Lx and
Ly are not quantized. Thus we can visualise the angular momentum vector
sweeping out in all possible direction in the xy plane.
Having analysed the angular part of the wavefunction and some of its
implications, let us now consider the radial part of the eigenfunctions for a
spherically symmetric potential.
2 1 d 2 dR (r ) 2 l ( l 1)
l 3 r V (r ) R(r ) E R(r )
2 r 2 dr dr 2 r 2
(8.44a)
l 2
This is a one-dimensional eigenvalue equation for the radial eigenfunction
R(r ) . The actual solution depends upon the form of potential energy function
V (r ) . However, the effective potential energy of the particle is
l 1
2 l (l 1)
Veff (r ) V (r ) (8.44b)
2 r 2
r
Thus, there is an extra term in the form of repulsive potential energy
l (l 1)
Fig. 8.3: The variation of (l (l 1) 2 / 2r 2 ) which increases with l (see Fig. 8.3, where we plot
l ( l 1) r2
with r for some
r2 as a function of the radial distance). You can see that this term decreases the
values of l. probability of finding the particle near the centre of force. This term is also
known as the centrifugal potential energy, or the centrifugal barrier.
The origin of the centrifugal term can be understand in the following manner
using classical correspondence. For a particle of mass moving in a circular
orbit of radius r , classically, there is a centrifugal force directed radially
outward. The magnitude of the force is v 2 / L2 r 3 , where L vr for a
circular orbit. The potential corresponding to such a force is
L2 / 2r 2 (since F V / r ) . In quantum mechanics we must replace L2 by its
eigenvalue l (l 1) 2 , hence we obtain the quantum mechanical expression for
the centrifugal potential.
For bound particles (such as a simple harmonic oscillator), the values of
E (eigenvalues) are discrete. Otherwise E varies in a continuous manner. But
whatever be the form of V (r ) , as long as it is spherically symmetric, the
angular part of the eigenfunction of the particle is given by the spherical
harmonics Yl ,ml (, ) .
132
Unit 8 Spherically Symmetric Potentials
8.5 SUMMARY
In general, the potential in which a particle moves in, in a three-
dimensional space is a function of all three spatial coordinates.
However, a spherically symmetric potential depends only upon the
radial coordinate r and is independent of the polar coordinates and
( V (r , , ) V (r ) ).In this unit we have discussed the quantum
mechanical behaviour of a particle having constant total energy and
moving under a three-dimensional, spherically symmetric
potential.
In classical mechanics, the angular momentum L of such a particle is
a constant of motion. However, in quantum
mechanics all the three
components Lx , Ly and Lz of the vector L cannot be constants of
motion simultaneously due to the fact the these three components
do
not commute among themselves.
However, the magnitude of L or L2
and one of the components of L (which we have taken as Lz ) can be
a constant of motion.
For a spherically symmetric potential V (r ) the steady state
Schrodinger equation is
r 2 2 (E V (r )) r 2
r
r 2
1 1 2
(sin )
sin sin 2 2
Where (r , , ) .
The angular momentum operators L̂2 and L̂z commute with the
Hamiltonian. Therefore the expectation value of the square of the
angular momentum is a constant of motion for a central potential.
(r , , ) can be separated in the variables r , and as follows:
(r , , ) R (r ) Y (, )
Where R(r ) is the radial component and Y ( , ) is the angular
component of the wave function.
The stationary state Schrodinger equation reduces to the following two
ODEs:
1 2 R(r ) 2 K
r (E V (r )) R (r ) 0
r 2 r 2 r 2 r2
And
1 Y (, ) 1 2Y (, )
sin K Y (, )
sin sin 2 2
where K is a constant.
The solutions Y (, ) of the angular equation are the spherical
harmonics Yl ,ml (, ) which are the eigenfunctions of L̂2 and L̂z :
Lˆ2 Yl ,ml (, ) l ( l 1) 2 Yl ,ml (, ) with l 0,1,2,..... 133
Block 2 Applications of Quantum Mechanics
Lˆz Yl ,ml (, ) m l Yl ,ml (, )
For a given integer l there will be the following (2l 1) values of ml :
l , l 1, l 2,...,0,..., l 1, l
Hence we can say that the eigenfunctions Yl ,ml (, ) are ( 2l 1) fold
degenerate. The parity of Yl ,ml (, ) depends only on the value of l and
is given by (1)l . Hence it is odd for odd values of l and even for even
values of l.
For ml 0
1/ 2
2l 1 (l ml )!
Yl ,ml (, ) ( 1)ml Pl ml (cos ) e iml
4 (l ml )!
Pl ml (cos ) are the associated Legendre functions and
ml d ml
Pl (cos ) sin ml
Pl (cos )
dv ml
Where Pl (cos ) are the Legendre functions.
And
Yl ,ml (, ) 1ml Yl ,ml (, )*
In the vector model of the angular momentum the angular momentum
of the particle in motion is given by a vector L of length [l (l 1)]1 / 2 .
Since L̂z is quantized, the vector L can make only certain quantized
angles with the z-axis; the angle , between L and Lz can take only
discrete
values. This phenomenon of the quantization of the direction
of L with respect to one of the coordinate axes, is known as space
quantization.
The effective potential energy of the particle in a spherically
symmetric potential is
2 (l 1)
Veff (r ) V (r )
2 r 2
The repulsive potential energy (l (l 1) 2 / 2r 2 ) which increases with l
decreases the probability of finding the particle near the centre of force
is called the centrifugal barrier.
4. Show that the spherical harmonics Y1,0 (, ) , Y1,1(, ) and Y1,1(, ) are
normalized and orthogonal to each other.
1
5. Use the Legendre polynomial P2 ( x ) 3 x 2 1 to construct
2
Y2 ,0 (, ) , Y2 ,1 (, ) and Y2 ,2 (, ) .
1 1
In spherical polar coordinates eˆr eˆ eˆ
r r r sin
1 1
Therefore, Lˆ ireˆ r eˆ eˆ (eˆ r eˆ r 0)
r sin
1 ˆ 1 1
ir eˆ e i eˆ eˆ
r r sin sin
1 1
Hence Lˆ2 Lˆ..Lˆ 2 eˆ eˆ . eˆ eˆ (i)
sin sin
1
2 eˆ . eˆ eˆ . eˆ
sin
(ii)
1 1 1
eˆ . eˆ eˆ . eˆ
sin sin sin
To simplify Eq. (ii), the partial derivatives are carried out first and then
the scalar product is taken. The unit vectors eˆ r , eˆ , eˆ are orthonormal
and derivatives of the unit vectors are given as
eˆ eˆr ; eˆ eˆ cos ; eˆ 0;
eˆ (eˆr sin eˆ cos ) (iii)
2 eˆ 2
ˆ ˆ
e . e eˆ .eˆ
eˆ . (iv)
2 2
135
Block 2 Applications of Quantum Mechanics
eˆ 1 1
ˆ ˆ
e . e
1
eˆ . eˆ
sin
sin sin
eˆ 1
eˆ .
sin
eˆ .eˆ
1
sin
eˆ.eˆr sin1 eˆ.eˆ sin1
0
1 1 eˆ 1 2
eˆ . eˆ eˆ . eˆ
sin sin sin
1 1 2
eˆ . (eˆ r sin eˆ cos ) eˆ
sin sin
cos
sin
1 1 1 eˆ 1 2
eˆ . eˆ eˆ. eˆ
sin sin sin 2 sin 2 2
1 1 2
eˆ.
eˆ cos
eˆ
sin 2 sin 2 2
1 2
sin 2 2
b) Now
2 2
[Hˆ , Lˆ2 ] V (r ), L2
2
2 1 2 Lˆ2
r V (r ), Lˆ2 (Using Eq. 8.6a)
2 r r r 2r
2 2
136
Unit 8 Spherically Symmetric Potentials
Similarly,
2 1 2 Lˆ2
[Hˆ , Lˆz ] r V (r ), Lˆz 0( [Lˆ2 , Lˆz ] 0)
2 r r r 2r
2 2
d dv d d
2. We can write sin
d d dv dv
and
d d d d
sin sin 2 (1 cos 2 ) (1 v 2 )
d dv dv dv
d dP (v )
(1 v 2 ) (1 v 2 ) K P (v ) (1 v 2 ) ml2 P (v )
dv dv
or (1 v 2 )
d
dv
(1 v 2 )
dP (v )
dv
K (1 v 2 ) ml2 P (v ) 0
Dividing by (1 v 2 ) , we get
2
d (1 v 2 ) dP (v ) K ml P (v ) 0
dv dv (1 v 2 )
d ml
( x ) 1 x 2
ml ml 2
3. a) Pl Pl ( x ) gives us
dx ml
P10 ( x ) 1 x 2 P1( x ) x
0
d
P11( x ) 1 x 2 P1( x ) 1 x 2
1 2 1 2
dx
P11(cos ) sin
3 1 / 2
Y1,0 (, ) cos
4
1/ 2
3 (0)! 3 1/ 2
Y1,1 (, ) sin e i sin e i
4 ( 2)! 8
137
Block 2 Applications of Quantum Mechanics
3 1/ 2
Y1,1(, ) 11Y1,1(, )* sin e i
8
i
or Yl ,ml (, ) c Yl ,ml (, )
2
c ml h / 2 ml
2
15
Let I1 Y2*,2 Y2,2 sin d d
2 sin 4 sin d
32
0 0 0
1
15
16 (1 2 2 2 ) d where cos
1
15 4 2 15 (15 10 3)
or I1 2 1
16 3 5 8 15
Hence proved.
Next we have to show that Y2*,2 (, )Y2,2 ( ) d 0 .
2 2
15
Let I2 Y2*,2 Y2,2 sin d d
32 sin 4 e 4i d d
0 0 0 0
2
Now e 4id 0, I2 0 .
0
Hence proved.
5. Replacing by and by we obtain
1/ 2
15
Y2,1( , ) sin ( ) cos ( ) e i ( )
8
1/ 2
15
sin cos e i Y2,1(, )
8
138
Unit 8 Spherically Symmetric Potentials
Hence the parity of Y2,1(, ) is even.
Terminal Questions
1. i) [Lˆz , xˆ ] [ xˆ pˆ y yˆ pˆ x , xˆ ] [ xˆ pˆ y , xˆ ] [ yˆ pˆ x , x ] yˆ [ pˆ x , xˆ ] i yˆ
xˆ [ xˆpˆ y yˆ pˆ x , xˆ ] [ xˆ pˆ y yˆ pˆ x , xˆ ] xˆ
yˆ [ xˆ pˆ y yˆ pˆ x , yˆ ] [ xˆpˆ y yˆ pˆ x , yˆ ] yˆ
zˆ[ xˆ pˆ y yˆ pˆ x , zˆ ] [ xˆ v y yˆ pˆ x , zˆ ] zˆ
( xˆ yˆ yˆ xˆ ) i ( yˆ xˆ xˆ yˆ ) i 0
Lˆ x [ i L y ] i Lˆ y Lˆ x Lˆ y i Lˆ x i Lˆ x Lˆ y 0
Lˆ2
2. Let the eigenfunction be (r , , ) R (r ) Y (, ) . Now Hˆ , the steady
2I
state Schrodinger equation is:
Hˆ (r , , ) E(r , , )
where E is the energy eigenvalue. As you know, the operator L̂2 acts only
on the angular part of the wave function, so
Lˆ2 Lˆ2
Hˆ (r , , ) (r , , ) R(r ) Y (, )
2I 2I
Lˆ2
Y (, ) EY (, )
2I
You already know that the solutions of the ODE Lˆ2 Y (, ) EY (, ) are
the spherical harmonics
Lˆ2 l ( l 1) 2
Yl ,ml (, ) Yl ,ml (, ) EYl ,ml (, )
2I 2I
139
Block 2 Applications of Quantum Mechanics
So the energy eigenvalues are
l (l 1) 2
El with l 0,1,2,.....
2I
And the energy eigenfunctions are Yl ,ml (, ) with l 0,1,2,..... For each
value of l, (2l 1) values of ml : l , l 1, l 2,...,0,..., l 1, l .
So while the energy depends only on the value of l, each energy eigen
state is (2l 1) -fold degenerate.
For l 0 , ml 0 , degeneracy is 1.
2 2
3. Y2,m;l ( , )
ml 2
15 15 5
2 sin2 cos2 2 sin4 (3 cos2 1)2
8 32 16
5 5
[6 cos4 6 cos2 4 6 sin2 cos2 ]
16 4
1
2
You may note that the sum Yl ,m l (, ) is always spherically
m l 1
symmetric.
2 2
Yl ,ml ( , ) sin dd 1
0 0
2 2
2 3
Y1,0 ( , ) sin dd cos2 sin d d
0 0 4
0 0
3 1
cos3 02
4 3 0
3 2
2 1
4 3
1 cos sin d d
2
3 2
8
140 0 0
Unit 8 Spherically Symmetric Potentials
3 1
cos cos3 02
8 3 0
3 4
2 1
8 3
2 2 3
2
3
8 d 1
Y 1, 1 ( , ) sin d d sin d
0 0 0 0
2 2
3 2 i
Y *1,0 ( , )Y1,1( , ) sin dd
4 2
cos sin d e d
0 0 0 0
2
3 1 3 i
sin e d 0
4 2 3 0 0
Similarly:
2 3
2
2 i
Y *1,0 ( , )Y1,1( , ) sin dd
4 2
cos sin d e d
0 0 0 0
2
1
3 3 i
3 sin e d 0
4 2 0 0
2 3
2
3 2i
Y *
1,1 ( , )Y1,1( , ) sin d d
8 sin d e d
0 0 0 0
2
2i
3 1 3 e
cos cos 2i 0
4 2 3 0 0
d ml
( x ) 1 x 2
ml ml 2
5. Using Pl Pl ( x ) we get
dx ml
1
P20 ( x ) 1 x 2 P2 ( x ) 3 x 2 1
0
2
P21( x ) 1 x 2 P2 ( x ) 31 x 2
d
1 2 1 2
x
dx
2 2 d2
P22 ( x ) 1 x 2 P2 ( x ) 31 x 2
dx 2
So,
141
Block 2 Applications of Quantum Mechanics
5 1/ 2 1 1/ 2
Y2 ,0 (, ) 3 cos 2 1 5 3 cos 2 1
4 2 16
1/ 2
5 (1)!
Y2 ,1 (, ) 3 sin cos e i
4 (3)!
1/ 2
15
sin cos e i
8
1/ 2 1/ 2
5 (0)! 15
Y2 ,2 (, ) 3 sin 2 e 2i sin 2 e 2i
4 ( 4)! 32
142
Unit 9 The Hydrogen Atom
UNIT 9
THE HYDROGEN
ATOM
Structure
9.1 Introduction Degeneracy of the Eigenfunctions
Expected Learning Outcomes Radial Probability Density
9.2 Schrödinger Equation for 9.4 Spectra of the Hydrogen Atom
the Hydrogen Atom Quantum Numbers and Constants of
9.3 Solution of the Radial Equation Motion
Asymptotic Properties of the Radial 9.5 Summary
Wave Function 9.6 Terminal Questions
Power Series Solution 9.7 Solutions and Answers
Eigenfunctions
Bound States and Continuum States
9.1 INTRODUCTION
When quantum mechanics was developed in the 1920s, one of its first (and
also one of the most important) applications was to understand hydrogen and
hydrogen like atoms (atoms with one valence electrons). In this unit, our main
focus will be on the hydrogen atom. In the previous Unit we discussed the
motion of a particle in a spherically symmetric potential. We had separated the
Schrödinger equation for a spherically symmetric potential V (r ) into radial and
angular coordinates. As we saw, the spherical harmonics are the
eigenfunctions of the angular part of the Schrödinger equation. The solution of
the radial equation depends on the particular potential function.
In this Unit we extend the ideas developed in the previous unit to the hydrogen
atom. As you know, a hydrogen atom consists of a proton and an electron
moving in the Coulomb potential of the proton. The motion of an electron in
the Coulomb potential of the nucleus is also referred to as the Kepler problem
of quantum mechanics – it is exactly solvable. You know that the Coulomb
e2
potential of the proton at a distance r is V (r ) . Hence the potential is
4 0 r
spherically symmetric.
In Sec. 9.2 we write down the stationary state Schrödinger equation for the
Hydrogen atom which is a two body system comprising a proton and an
electron. The equation is then reduced to two three-dimensional Schrödinger
equations in the centre-of mass and relative coordinates. The general solution
for the stationary state wave function comprises the radial and angular parts.
In Sec. 9.3 we solve the stationary state Schrödinger equation for the radial 143
Block 2 Applications of Quantum Mechanics
part of the three-dimensional Schrödinger equation to obtain eigenfucntions
and eigen energies for the stationary states of the hydrogen atom. As for the
simple harmonic oscillator, we rewrite the Schrödinger equation in terms of
dimensionless variables and study the differential equations in its asymptotic
limits to arrive at a trial solution considering the properties of a physically
acceptable wave function. We use the power series method to obtain the
energy eigenfunctions and eigenvalues. We study the degeneracy of the eigen
states and also discuss the continuum states of the hydrogen atom. In
Sec. 9.4 we discuss the Hydrogen atom spectra and the significance of the
quantum numbers.
Expected Learning Outcomes
After studying this unit, you should be able to:
reduce the two-body hydrogen atom system to two one-body systems;
solve the stationary state Schrödinger equation for the radial wave
function for the hydrogen atom;
obtain the eigenfunctions and energy eigenvalues for the stationary states
of a hydrogen atom;
explain the spectra of the hydrogen atom; and
specify the constants of motion and the corresponding quantum numbers
for the hydrogen atom problem.
Hence, in three-dimensions
M
1 R (9.8)
mM
where
iˆ jˆ kˆ (9.9)
x y z
and ( x1, y1, z1), ( x, y , z ) and ( X ,Y , Z ) are the components of r1, r and R,
respectively. Similarly, from Eq. (9.5) we obtain
m
2 R (9.10)
mM
Eqs. (9.8) and (9.10) yield
M 2 2 M
12 R 2 R . 2 (9.11a)
mM mM
and
m 2 2 m
22 R 2 R . 2 (9.11b)
mM mM
Putting the expressions for 12 and 22 from Eqs. (9.11a and b) into Eq. (9.1b)
we get
2 2 2 1 1 2 e2
2(M m ) R 2 m M r (R, r ) ET (R, r )
(9.12)
where for our convenience we have replaced e 2 / 4 0 by only e 2 with
e 2 2.31 10 28 J m. Eq. (9.12) is separable in the coordinates R and r.
Taking
(R, r ) (R ) (r ) (9.13) 145
Block 2 Applications of Quantum Mechanics
we find that (R ) and (r ) are the respective solutions of the following three-
dimensional differential equations
2
2 (R ) E H (R ) (9.14)
2(M m ) R
2 2 e2
and ( r ) ( r ) E ( r ) (9.15a)
2 r
1 1 1
where (9.15b)
m M
and
ET E E H (9.16)
As you know, is the reduced mass of the system.
Eq. (9.14) shows that a particle of mass (m + M), which is the total mass of the
hydrogen atom, is moving freely in a three-dimensional space and its total
energy is EH (with zero potential energy). This is a problem that you have
already solved in Unit 5. Its eigenfunctions are given by plane waves
(R ) e iK .R (9.17)
2K 2
With EH (9.18)
2( m M )
The eigenvalue E H and the corresponding quantum number K vary in
continuous manner.
On the other hand, Eq. (9.15a) describes the motion of a particle of mass
having potential energy e 2 / r with respect to a fixed centre. Thus, by the
above procedure we have reduced a two-body system into two one-body
systems, one of mass (m + M) which moves freely in space and other of mass
and charge e which moves under an attractive potential e 2 / r . You should
note that in the present model the relative motion of electron and proton with
respect to each other has been replaced by the motion of a particle of mass
with respect to a fixed centre of force.
Now Eq. (9.15a) is exactly the same as Eq. (8.1) with V (r ) e 2 / r . Hence
the eigenfunctions of the particle of mass , which are also known as the
eigenfunctions of the hydrogen atom, are given by
(r , , ) R (r )Yl , ml (, ) (9.19)
Substituting K l (l 1) and V (r ) e 2 / r in Eq. (8.5), the radial function
R(r ) is the solution of the following one-dimensional differential equation
2 1 d 2 dR (r ) e 2 2 l (l 1)
r R (r ) ER ( r )
2 r 2 dr dr r 2 r 2
(9.20)
The above equation has been obtained from Eq. (8.44a) by taking
V (r ) e 2 / r . The effective potential energy in this case is
e 2 2 l (l 1)
Veff (r ) (9.21)
146 r 2 r 2
Unit 9 The Hydrogen Atom
2 l (l 1)
Near the origin is much larger than e 2 / r .
2 r 2
It is possible to get both bound and continuum states for the Coulomb
potential. For E 0 one gets states with continuous values of E, which
describe electron-proton scattering. But with E 0 the states have discrete
values of E, which are the bound states of the hydrogen atom.
1 d 2 dR (r ) 2e 2 1 l (l 1) 2E
r 2 R(r ) 2 R(r )
2
r dr dr r r 2
(9.22)
d 2u 2E 2e 2 1 l (l 1)
u (9.25)
dr 2 2 2 r r2
2 d 2u 2e 2 2 1 2 l (l 1)
1 u (9.26)
2E dr 2 2 2E r 2E r 2
2E
Defining a constant k , which as you can see is real for the bound
2
states because E < 0, we introduce a dimensionless variable kr and:
du du d du d 2u d 2 u d d 2u 2E d 2u
k ; k k2
dr d dr d dr 2 d 2 dr d 2 2 d 2
(9.27)
Therefore Eq. (9.26) is
d 2u 2e 2 1 l (l 1)
1 u (9.28)
d 2 2k 2
2e 2
We define 0 to write Eq. (9.28) as
2k
d 2u 0 l (l 1)
1 u (9.29)
d 2 2
SAQ 1
With u rR(r ) , show that Eq. (9.23) reduces to Eq. (9.25).
147
Block 2 Applications of Quantum Mechanics
9.3.1 Asymptotic Properties of the Radial Wave
Function
We now examine the properties of the solutions of Eq. (9.29) for and
0.
For
d 2u 0 l (l 1) d 2u
1 u u (9.30a)
d 2 2 d 2
And the general solution is:
u Ae Be (9.30b)
Since the solution should not diverge, we must have A 0 and therefore
u Be (9.31)
For 0
d 2u l (l 1) 0 d 2u l (l 1)
1 0 u u (9.30a)
d 2 2 d 2 2
And the general solution is:
u C l D l 1 (9.30b)
Eq. (9.30a) does not Since the solution should not diverge as 0 , we must have C 0 (see
hold at ρ=0 , though the margin remark) and therefore
Eq. (9.31) still holds)
u D l 1 (9.31)
Now that we know the asymptotic behaviour, we can write the general solution
for Eq. (9.29) as
u e l 1F () (9.32)
The first factor ensures that the solution does not diverge and the
second factor ensures that the 0 solution is finite. Also, an
exponential function decays faster than any polynomial and therefore in
the limit the solution is dominated by the exponential factor.
Next, we try to determine the function F () . Substituting from Eq. (9.32) into
Eq. (9.29) we get the following ODE for F () (SAQ 2):
d 2F dF
2(l 1) 2 0 2(l 1)F 0 (9.33)
d 2 d
SAQ 2
Show that the ODE for F () is
d 2F dF
2(l 1) 2 0 2(l 1)F 0
d 2 d
This value of m mmax is the highest power of in the power series for
F ( ) :
mmax
F ( ) cmm (9.42b)
m 0,1,2,...
2E
with k . Using 0 2n in Eq. (9.43) we get:
2
2e 2 e 2 1
k k (9.44)
2 ( 2n ) 2 n
2
a0 (9.45)
μ e2
It is interesting to note that a0 is equal to the radius of the first orbit of the
electron in a hydrogen atom for the model proposed by Bohr, provided is
replaced by the rest mass of the electron m. Since the ratio of m / is very
close to unity (1.0005), we shall take a0 to be equal to the first Bohr radius
with 0.529 10 10 metre as its value. With this
1
k (9.46a)
a0 n
2E 1 1
or k2 where n 1,2,... (9.46b)
2 a02 n 2
Therefore the energy E of the hydrogen atom can take on discrete values
corresponding to the values of n 1,2,... Designating the eigen energy of the
hydrogen atom corresponding to any value of n by En , we get from Eq.
(9.46b)
150
Unit 9 The Hydrogen Atom
2 1 e4
En (9.47)
2 μa02 n 2 2 2 n 2
R
En (9.48a)
n2
me 4
where R (9.48b)
2 2
is the Rydberg constant.
SAQ 3
a) Obtain the value of the Rydberg constant in the units of electron volts and
m 1 .
b) Write down the energy for the ground state and first three excited states of
the hydrogen atom.
For each value of n the solution of the radial equation ( u e l 1F () )
designates an eigen state of the system defined by an eigenfunction which we
now write down.
9.3.3 Eigenfunctions
With 0 2n , the radial equation Eq. (9.29) reduces to
d 2u 2n l (l 1)
1 u (9.49)
d 2 2
The solution of Eq. (9.49) ( u e l 1F () ) clearly depends on the value of n
and l. For each set of values of n and l the solution of Eq. (9.49) can be
r
written as u n,l () where kr . Also from Eq. (9.24) u n,l () can be
a0n
written as
u n,l ()
u n,l () rR n,l (r ) R n,l (r ) (9.50)
r
where for a given value of n:
l n 1, n 2, n 3,...,0 (9.51)
This is in addition to what we had obtained for the spherical harmonics in Unit
8, where we found that the values of l are 0,1,2,3... Eq. (9.51) therefore sets
the upper value for l which is decided by the value of the principle quantum
number n for any given eigen state of the hydrogen atom. So for each value of
n, l 0,1,2,...( n 1) and we can write
r
with and n 1,2,... and for each value of n , l 0,1,2,...( n 1)
a0n 151
Block 2 Applications of Quantum Mechanics
F () is a polynomial of degree mmax n (l 1) and the recursion relation for
coefficients of the power series is
cm 1
2(l 1) 2m 2n cm (9.52b)
(m 1)(m 2l 2)
All the coefficients in Eq. (9.52b) upto mmax n (l 1) are written in terms of
c0 and c0 can be determined by applying the normalization condition
on each function R n,l ( r ) .
Let us write down the first of these eigen functions. For n 1 , the only
r
possible value of l is l 0 . With n 1 , and mmax 0 . So the power
a0
series for F () will have just one term and F () c 0 . So
e r / a0 r c 0 r / a
R1,0 ( r ) c 0 e 0 (9.53)
r a0 a 0
2
R1,0 (r )R1,0 (r )r 2 dr 1 c 02 e 2r / a0 r 2 dr 1 c 0
0 0
a0
And write
e r / a0 r 2
R1,0 (r ) c 0 e r / a0 (9.54a)
r a0 a03
The higher order radial eigenfunctions can be found in the same way.
1 r r / 2a0
R 2,0 (r ) 2 e (9.54b)
(2a0 )3 / 2 a0
1 r
R2,1(r ) e r / 2a0 (9.54c)
3/2 a0
3 (2a0 )
3/2
1 2r 2 r 2 r / 3a0
R3,0 (r ) 21 e (9.54d)
3a0 2
3a0 27 a0
3/2
1 4 2 r r r / 3a0
R3,1(r ) 1 e (9.54e)
3a0 9 a0 6a0
3/2
1 2 2 r 2 r / 3a0
R3,2 (r ) e (9.54f)
3a0 27 5 a02
152
In general the radial eigenfunctions of Eq. (9.52a) are given by
Unit 9 The Hydrogen Atom
l
r r
R n,l (r ) N n l exp Gn l (r / a0 ) (9.55)
na 0 a0
Rn,l (r )
R1,0 (r )
R 2,0 (r )
R3,0 (r )
R2,1(r )
SAQ 4
where R n, l (r ) and Yl , ml (, ) are given by Eq. (9.46) and Eq. (8.36),
respectively. These eigenfucntions form an orthonormal set, i.e.,
SAQ 5
a) List the eigenfunctions of the hydrogen atom for n 1, 2 .
b) Using Eqs. (9.54), (9.58) and (8.40) write down the eigenfunctions
100 , 200 , 211 .
100 is the eigenfunction for the lowest energy state or ground-state of the
hydrogen atom. A few hydrogen atom wave functions are given in the table
below:
1 1
100 e r / a0 200 2 r / a0 e r / 2a0
a03 / 2 3
4 2a0 / 2
1 1
210 r / a0 e r / 2a0 cos 211 r / a0 e r / 2a0 sin e i
4 2a03 / 2 8 a03 / 2
r2 2
300
1
27 18
r
2 e r / 3 a0 310 r / a0 6 r / a0 e r / 3a0 cos
81 3a03 / 2 a0 a02 a03 / 2
311
1
3 / 2
r / a0 6 r / a0 e r / 3a0 sin e i 320 1
3 / 2
r / a0 2 e r / 3a 3 cos2 1
81 a0 81 6a0
1 1
32 1 r / a0 2 e r / 3a0 sin cos e i 322 r / a0 2 e r / 3a0 sin2 e 2i
81 a03 / 2 162 a03 / 2
E n in eV
Continuum States
0
0.85 n4
1 .5 n3
3 .4 n2
13.6 n 1
l 0 l 1 l 2 l 3
And if we take into account the two-valuedness called spin, which you will
study in Unit 14, the total degeneracy is 2n 2 .
155
Block 2 Applications of Quantum Mechanics
9.3.6 Radial Probability Density
2
Probability nlml dV . (9.61a)
The volume element dV r 2 sin drdd And we know that when this
probability is integrated over all space, the value is 1:
2 2
nlm l r 2 sin drdd 1 (9.61b)
r 0 0 0
2
P nlml (r , , ) nlml
is the probability density or the probability per unit
volume. In general (Eq. 8.36), the wave function nlml is
For example the radial probability density for the 100 state is:
2
1 4r 2 2r / a0
P100 (r )dr 4r 2 n 00 2
r 2 e r / a0 e (9.64)
a 3 a03
0
In TQ 3 you will calculate the most probable location of the electron in the
100 state and see that it is equal to one Bohr radius.
The radial probability distribution functions for a few zero orbital angular
momentum states is shown in the figure below.
156
Unit 9 The Hydrogen Atom
P100
P200 P300
Fig. 9.3: Radial probability distributions for the 100 , 200 and 300 states.
SAQ 6
1 1
E R (9.61)
n2 n2
2 1
1 1
1.097 107 2 2 m 1 (9.62)
n
2 n1
Due
to spherically symmetric potential the angular momentum of the object
L becomes a constant of motion. However, due
to non-commutability of
Lx , Ly and Lz the angular momentum vector L is not a constant of motion in
quantum mechanics but as you have seen, L2 is a constant of motion. This
gives rise to another quantum number l , which varies in a discrete manner and
is a positive integer. Since l is connected with the orbital motion of the object
it is called orbital quantum number or the azimuthal quantum number.
From Eq. (9.45) we can show that l is less than n and for a given value of n it
takes the following values:
0,1, 2,..., n 1 (9.63)
Since a spherically
symmetric potential is also axially symmetric, the
z component of L also becomes a constant of motion and gives rise to a third
quantum number ml . It can take negative as well as positive number n .
However, it can be shown that if the atom is placed under a magnetic field, its
energy depends upon ml . Hence ml is known as magnetic quantum number.
For a given value of l , the permissible values of ml are
l , l 1,...., 0,1, 2,..., l 1, l (9.64)
SAQ 7
158
Unit 9 The Hydrogen Atom
9.5 SUMMARY
A hydrogen atom in a two-particle system consisting of a proton(of
mass M) and an electron(of mass m) and its stationary state
Schrödinger equation is a six-dimensional differential equation.
However, it can be separated into two three-dimensional differential
equations:
-One corresponding to the motion of a free particle having mass
( m M ) . Its solutions are plane waves e iKR , where the energy
quantum number K varies in a continuous manner and is related to
E H by Eq. (9.18b).
-The second three-dimensional differential equation describes the
motion of a particle of mass (reduced mass of the system) having a
charge e in a spherically symmetric potential (Coulomb potential) due
to a fixed center of force having charge e . This differential equation
again separates into three one-dimensional differential equations, one
for each spherical polar coordinate r , and . These degrees of
freedom given rise to three quantum numbers n, l and ml .
The nature of the radial wave function R(r ) depends upon whether the
state is a bound state or a continuum state. For bound states the
2 1 / 2 r
eigenfunction varies as exp E at large value of r. Hence
2
a0
the probability of finding the particle goes to zero as r increases to .
On the other hand, for continuum states the probability remains finite
even as r goes to infinity. At small and intermediate values of
r , different spherically symmetric potentials give rise to different radial
functions. In this unit we have considered Coulomb potential,
appropriate to a hydrogen atom.
The angular eigenfunctions of the hydrogen atom are again spherical
harmonics and the radial eigenfunctions for bound states are given in
terms of the associated Laguerre polynomials. The quantum number n
takes only positive integer values excluding zero. For a given value of
n, the angular momentum quantum number l takes n values given
by
l 0,1, ...., n 1
For each value of l the magnetic quantum number ml takes the
values
ml 1, l 1,.... 0, l , ...l 1, l
3. Obtain the most probable value and expectation value of r for the ground
state of a hydrogen atom.
4. Consider an initial state of the hydrogen atom:
(r ,0)
1
10
3100 200 2 210 2 211
Determine a) the expectation value of the energy at t = 0 and b)the wave
function (r , t ) .
1 d 2u 2e 2 1 l (l 1) 2E
r u 2 u (iv)
2
r dr 2 r r 2
d 2u 2E 2e 2 1 l (l 1)
or u (v)
dr 2 2 2 r r2
2. Using u e l 1F () we can write
du dF
e l 1F () (l 1)e l F () e l 1 (i)
d d
d 2u dF
e l 1F (l 1)e l F e l 1
d 2 d
dF
(l 1)e l F l (l 1)e l 1F (l 1)e l
d
dF dF d 2F
e l 1 (l 1)e l e l 1
d d d 2
e l 2(l 1) l (l 1) 1 F
dF d 2F
e l 2(l 1) 2 e l (ii)
d d 2
e l 2(l 1) l (l 1) 1 F
dF d 2F
e l 2(l 1) 2 e l
d d 2
l ( l 1)
e l 1 1 0 F
2
d 2F dF
or 2(l 1) 2 0 2(l 1)F 0
d 2 d
me 4
3. a) R 2.18 10 18 Joules 13.6 eV ( e 2 2.31 10 28 J m)
2 2
me 4 1
also in units of m1, R 2 ch
1.10 107 m1 an accurate value of
2
the Rydberg constant is
R 1.09737373 10 7 m 1 .
b) Using the results of SAQ 3a and Eq. (9.48a), we get the ground state
energy to be 161
Block 2 Applications of Quantum Mechanics
R
The ground state energy E1 13.6 eV
12
R
The first excited state energy E 2 3.4 eV
22
R
The second excited state energy E 3 1.5 eV
32
R
The third excited state energy E 4 0.85 eV
42
e l 1 n l 1 m
4. a) We use Rn,l (r )
r
c m (Eq. 9.52a) with n 2 , l 0 ,
m 0,1,2,...
r r
n l 1 2 0 1 1 and to write
a0 n 2a0
e r / 2a0 r
1
e r / 2a0 r
R 2,0 (r )
r
2a0
cm m
m 0. 2a0 c 0 c1 2a
0
(i)
Using Eq. (9.52b) we get n 2 , l 0 , m 0
2 4
c1 c o c1 c o (ii)
2
Using Eq. (ii) in Eq. (i) we get
e r / 2a0 r e r / 2a0 r
R 2,0 (r ) c 0 c 0 2a c 0 2
2a0 0 4 a 0 a 0
e l 1 n l 1 m
Using Rn,l (r )
r
c m (Eq. 9.52a) with n 2 , l 1 ,
m 0,1,2,...
r r
n l 1 2 1 1 0 and we get
a0 n 2a0
2
e r / 2a0 r 0 re r / 2a0
R 2,1(r )
r
2a0 m 0.
c m m c 0
4a02
(iv)
c 02
8a03 1 or c 0
2
(i)
16a02 a0
0 0
c 02
So 24a05 1 or c0
2
(iii)
16a04 3a0
2 re r / 2a0 1 re r / 2a0
So R 2,1( r ) (iv)
3a 4a02 2a0 3 / 2 3a0
0
1 r
c) * (r )
R 20 R10 (r ) r 2 dr
2a06
1/ 2
2 a0 r 2e (3r / 2a0 ) dr
0 0
1 2! 1 3!
2 0
2 a03 3
3 a0 3 4
2a0 2a0
5. a) For n 1, l 0 and ml 0 so the eigenfunction is 100
For n 2 and l 0,1. For l 0 , ml 0 . For l 1 , ml 1,0,1. So
the wave functions are
200 , 211, 210 and 211 .
2 1 1 / 2
b) 100 R1, 0Y0,0 e r / a0
a03 4
1
e r / a0
a03
1 r r / 2a0 1 1 / 2
200 R 2, 0Y0,0 2 e
4
3/2 a
( 2a 0 ) 0
1 r r / 2a0
2 e
32a03 a0
1 r 3 1/ 2
211 R2,1Y1,1 e r / 2a0 sin e i
8
( 2a )3/2 a 3
0 0
1/ 2
1 r r / 2a0
e sin e i
64a 3 a0
0
6. The probability of the electron being within a distance r from the proton in
the 100 state is
163
Block 2 Applications of Quantum Mechanics
r r
4
P P100 (r )dr
a03 r 2e 2r / a dr
0
0 0
4 a3 a a2 a3
0 0 r 2 e 2r / a0 0 re 2r / a0 0 e 2r / a0
a03 4 2 2 4
r r2
1 e 2r / a0 1 2 2 (i)
a0 a02
The probability of finding the electron within a distance r a0 is
obtained by substituting r a0 in Eq. (i) :
P (r a0 ) 1 e 2 1 2 2 1 5e 2 .323
4e 2 e2 2 4
1
2 E1
a0 and E1 e
a03 2 2 a0 e 2 2 2
a0
Since kinetic energy + potential energy = total energy
e2 e2 e2
K .E. E1 V (r ) E1
2a0 a0 2a0
2. Let the size of the atom be R0 . since the electron is inside the atom, the
uncertainty in the momentum is p / R0 . The linear momentum of
magnitude p can be in any direction so its components can have values
164
Unit 9 The Hydrogen Atom
from p to p . Hence the uncertainty in momentum is also approximately
p . Hence we take p p . Now we take
K .E.
p 2
2
K .E.
2 2 R02
2 e2
E K .E . V at R0 .
2 R0 2 R0
dE 2 e2
Now 0 for a stable atom.
dR0 R03 R02
Hence
2
R0 a0 .
e2
Hence the size of the most stable atom is the first Bohr radius itself.
3. The probability of finding the electron between r and r + dr is given by
1 4 2 2r / a 0
100 (r ) r 2 4dr e 2r / a0 r 2 4dr r e dr .
a03 a03
2 2
r 2r e 2r / a0 0 or r a0
a0
However the average value of r is given by
r 100 (r ) 2 r r 2 dr sin d d
1
4 e 2r / a0 r dr
3
3
a0
0
4 6 3
a0 .
a03 2
4 2
a0
4. a)
E Hˆ * (r ,0)Hˆ (r ,0)d 3 r
Hˆ (r ,0)
1
Hˆ 3 100 200 2 210 2 211
10
1
3E1100 E 2 200 2E 2 2E 2 211
10
Also
* (r ,0)
1
*
3100 *200 2 *210 2 *211
10
Using the property of orthogonality of the eigenfunctions (Eq. 9.58) and the
value of the eigen energies (Eq. 9.49a) we get
E
1
10
3100
*
*200 2 *210 2 *211
3E1100 E2 200 2E 2 2E2 211 d 3r 165
Block 2 Applications of Quantum Mechanics
1 1
3E1 E2 4E 2 2E 2 3E1 7E2
10 10
R 7
3 6.46 eV
10 4
iHˆ t
b) (r , t ) e (r ,0)
iHˆ t
e
1
10
3100 200 2 210 2 211
iE t iE t
3 1 2 1 1 2
e 100 e 200 210 211
10 10 10 10
1
5. For the ground state 100 e r / a0 . Therefore
a03
2
r2 r 2 100
2
r 2 sin drdd
r 0 0 0
1 2
a03 r 0 0 0
r 4e 2r / a0 sin dr d d
4 4 2r / a0
r e dr 3a02
a03 r 0
d 2u 2mE l (l 1)
u
dr 2 2 r 2
d 2u 2mE
u
dr 2 2
2mE
Where k . Therefore
2
cos( kr )
Since the function diverges as r 0 , we must set A 0 so
r
that R(r ) is a square integrable function. So the solution is
sin( kr )
R( r ) B
r
nr
sin
R0
R( r ) N n
r
1
6
3(0) 200 7 ( 2 2 ) 211 2( 2 2 ) 211 4(2 2 ) 311
1
6
Lˆz (r ) Lˆz 3 200 7 211 2 211 4 311
1
6
3(0) 200 7 ( ) 211 2( ) 211 4( ) 311
6
7 211 2 211 4 311
Also
1
* (r ) 3 *200 7 *211 2 *211 4 311
6
*
So L̂2
1
36
3
7(2 2 ) 4(2 2 ) 16(2 2 ) 2
2
And
L̂z
7 4 16 19
36 36
N 2 *100 100d 3r 8 *210 210d 3 r 16 *211 211d 3 r 1
167
Block 2 Applications of Quantum Mechanics
1
N 2 1 8 16 1 or N
5
So (r )
1
5 100
2 2 210 4i 21 1
1
And * (r ) *100 2 2 * 210 4i * 21 1
5
1
5
Hˆ (r ) Hˆ 100 2 2 210 4i 21 1
1
E1100 2 2E 2 210 4i E 2 21 1
5
1
And Ĥ E1 8E2 16E2 1 E1 24E2 7 R
25 25 25
L̂2
2
25
(0) 8(2) 16(22 )
48 2
25
And
L̂z
0 0 16 16
25 25
168
Unit 8 Observables and Operators
FURTHER READINGS
169
Block 2 TABLE OF PHYSICAL CONSTANTS
Applications of Quantum Mechanics
h / 2 1.054 10 34 Js
me Electron rest mass 9.109 10 31 kg
170