QUANTUM MECHANICS

Wave equation
Time dependent Schrodinger equation
Linearity & superposition
Expectation values
Observables as operators
Stationary states and time evolution of stationary states
Eigenvalues & Eigenfunctions
Boundary conditions on wave function
Application of SE (Particle in a box, Potential barrier, one
dimensional harmonic oscillator)
 Quantum Mechanics/Physics
CENTRAL IDEA
Quantum physics deals with matter with wave properties. The
behavior of a particle is described with a wave function, using
Schrodinger's equation. The wave function is interpreted using
probability because we cannot say exactly where a particle is. We
judge where something is using generalized probability but cannot
perform a measurement without the collapse of the wave function .

Quantum physics:
What happens to physics when we give wave properties to matter
So it's described by something called a wave function
Ψ
“everything” about the system!
that's going to take the place of a position, a momentum and all those things
Instead of that we describe the behaviour of a particle by its wave function
 if we leave the particle alone, it behaves like a wave.
So we're just sitting there letting the system do whatever it wants to do and it's described
by its wave function.
However, if we perform a measurement, suddenly we get something called the collapse of
the wave function. So for example, if we've got a wave function that looks like that, and
then we perform a measurement and we say, is the particle between these two green lines?

Is or isn’t….not both
PROBABILITY
wave function will give us probabilities. It will say alright. If you did that
measurement 100 times, 6 times you're going to find that it was between the
green bars and the other 94 times you're going to find that it wasn't.
Since Ψ(x,t), describes a particle, its evolution in time under the action of
the wave equation describes the future history of the particle
Ψ(x,t) is determined by Ψ(x, t = 0)
Uncertainty built in from the beginning 3
Wave function is complex

is a positive real quantity: proportional to the probability density P of

finding the body described by
Than integral of 2 over all space must be finite—the body is
somewhere. Particle in certain region of x1 to x2

If Particle doesn't exist.

Normalization
if the particle exists somewhere at all times
2
r,t d 3r 1 or
or
all space

x, t
2
dx 1 - a wavefunction which obeys this
In 1D: condition is said to be normalized
Suppose we have a solution to the Sch. Eq. that is not normalized.
The recipe for normalization:
Calculate the normalization integral N 2
( x, t ) dx
Re-scale the wave function as 1
' r,t r,t
N
This procedure works because any solution of the S.Eq. being multiplied by a
constant remains a solution: the S..Eq. is linear and homogeneous.

Ex.1 Find the value of the normalization constant A for the wave function =
Axe-x2/2.

Ex.2: The wave function of a certain particle is = A cos2x for - /2 < x < /2. (a)
Find the value of A. (b) Find the probability that the particle be found between x =
0 and x = 4.
 The well behaved wave function must be:
1. be a continuous and single-valued function of all x and t (the
probability density must be uniquely defined)
2. have a continuous first derivative and single valued (the
exception - points where the potential is infinite)

3. Have a finite normalization integral (so we can define a

normalized probability)

(a) A sec x (b) A tan x (c) A ex2 (d) A e-x2

The wave function satisfies something called Schrodinger's
equation which kind of takes the place of conservation of energy
Time dependent Schrödinger Equation
Schrödinger developed the wave equation which can be solved to find the
wavefunction by translating the equation for energy of classical physics into
the language of waves
We assume that for a particle moving freely in the x direction is
specified by
or

since
then

differentiating once with respect to t,

differentiating for twice with respect to x,

or
or
7
 Total energy of the particle

then

Substitute the value of E and p2

Time-dependent Schrödinger equation in one dimension

Time-dependent Schrödinger equation in three dimension

Schrödinger’s equation cannot be derived from other basic principles

of physics; it is a basic principle in itself.
8
 Properties of
Wave functions add, not the probabilities
(i) Linearity and superposition
Linearity: An important properties of Schrodinger equation: it is linear in the ,
the equation has terms that contain and its derivatives but no terms independent
of or that involve higher powers of or its derivatives.

Superposition: If 1 and 2 are two solutions,

= a1 1 + a2 2 is also a solution; 1 and 2 obey the superposition principle.
Interference effects can occur for wave functions just as they can for light, sound, etc
Superposition's to the diffraction of an electron beam:
Slit 1 is open: probability density: P1 = I 1I =
2
1* 1

Slit 2 is open: probability density: P2 = I 2I =

2
2* 2

Both open, probability density at screen:

P = I I2 = I 1+ 2I
2 =( 1* + 2*)( 1+ 2)

= 1* 1 + 2* 2 + 1* 2 + 2* 1

= P1+ P2+ 1* 2 + 2* 1

Responsible for oscillations of the e- intensity at screen

(ii) Stationary state

Probability is independent of time

for every expectation value is constant in time

 EXPECTATION VALUES
How to extract information from a wave function
let us calculate the expectation value <x> of the position of a particle confined to
the x axis that is described by the wave function (x, t).
What is the average position x of a number of identical particles distributed along the
x axis in such a way that there are N1 particles at x1, N2 particles at x2, and so on?

When we are dealing with a single particle, we must replace the number Ni of
particles at xi by the probability Pi that the particle be found in an interval dx at xi.
This probability is

Expectation value
for position

Expectation value for any quantity

OPERATORS Another way to find expectation values

An operator tells us what operation to carry out on the quantity that follows it.
OPERATOR and expectation value
Because p and E can be replaced by their corresponding operators in an equation,
we can use these operators to obtain expectation values for p and E.
Physical Quantity Operators
Any measurement of the observable a corresponds to operator Â, the only
values that will ever be observed are the eigenvalues of Â, which satisfy the
eigenvalue equation ˆ A x, t A x, t

If a system is in a state described by a wave function (x,t), then the

average/expectation value of the observable a (measured once on many identical
systems) is given by ˆ
x, t A *
x, t dx
These are values of physical quantities that quantum a
*
x, t x, t dx
mechanics predicts and which, from experimental
point of view, are averages of multiple measurements

SCHRÖDINGER’S EQUATION: STEADY-STATE FORM

In many situations, the potential energy of a particle does not depend on time
explicitly; the forces that act on it, and hence U, vary with the position of the particle
only. When this is true, Schrödinger’s equation may be simplified by removing all
reference to t.
1D:

3D:
An important property of Schrödinger’s steady-state equation
is that, if it has one or more solutions for a given system,
each of these wave functions corresponds to a specific value
of the energy E. Thus energy quantization appears in wave
mechanics as a natural element of the theory, and energy
quantization in the physical world is revealed as a universal
phenomenon characteristic of all stable systems.

APPLICATION OF SCHRÖDINGER EQUATIONS

Particle in a box
Finite potential Well
Tunnelling
Harmonic Oscillator
Particle in a box with “Infinite Hard walls”
+ x 0 Boundary conditions and normalization determines

U(x) = 0 0 x L

+ x L
Since the walls are impenetrable, there is
zero probability of finding the particle
outside the box.
Zero probability means:
ψ(x) = 0, for x 0 and x L

The wave function must also be 0 at the

walls (x = 0 and x = L), since the
wavefunction must be continuous

Mathematically, ψ(0) = 0 and ψ(L) = 0

 Schrödinger Equation
2 2
x
2
U ( x) x E x
2m x
for Particle in a Box
For 0 < x < L, where U(x) = 0, the Schrödinger equation can
be expressed in the form
2 2
x
2
E x
2m x
We can re-write it as
2
x 2m E
2 2
x
x
2
x
2
k2 x
x
2m E
k2 2
 2
x 2
2
k x
x
The most general solution to this differential
equation is:
ψ(x) = A sin kx + B cos kx
A and B are constants which are determined from the
properties of the ψ as well as boundary and
normalization conditions
1. Sin(x) and Cos(x) are finite and single-valued functions

2. Boundary Condition: ψ(0) = ψ(L) = 0

• ψ(0) = A sin(k0) + B cos(k0) = 0 B = 0
ψ(x) = A sin(kx)
• ψ(L) = A sin(kL) = 0 sin(kL) = 0 kL = nπ, n = ±1, ±2…
 kn n n 1,2,3...
L
Particle in a Box
2
Energy 2 2 ( n) 2 2 2
kn L h2
Levels: En n2 n 2

2m 2m 2mL2 8mL2

• The allowed wave functions are given by

n
ψn(x) A sin x
L

• The normalized wave function:

2 n
ψn(x) sin x
L L
 2 n 2 2
ψn(x) sin x ψ4 ψ n(x)
L L ψ4
2
ψ3
ψ3
2
ψ2
ψ2
2
ψ1 ψ1

2 2 2 2
En n2 E0 n 2 , with E0
2m L2 2m L2
ground state (n 1) energy , E1 E0

19
19
Ex-1: e- in a 10nm wide Well with infinite barriers. Calculate E0 for L = 10 nm
2 2
3.14 2 (1.05 10 34 ) 2
E0
En 2
E0 n , where E1 E0 2 9.1 10 31 (10 10 9 ) 2
2mL2 E0 6 10 22
J 0.00375 eV 3.75 meV
1 meV 10-3 eV
Ex-2: Assume that a photon is absorbed, and the
electron is transferred from the ground state (n =
1) to the second excited state (n = 3). What was
the wavelengths of the photon?

Eground E1 E0 0.00375 eV
Third e xcite dstate is E3
E3 E0 3 2 9 0.00375 e V 0.0338 e V
(h ) E3 E1 0.0338 0.00375 0.030 e V
1240
λ 41333 nm 41 μm
0.03
Average Momentum of Particle in a Box (Infinite Potential Well)
problem L
* *
px ( x) ( x)dx
0
i x
2
L sin kx
2 L
[ sin kx] dx
0
L i x
L
2
k sin( kx) cos(kx)dx 0
L i 0
Note: the right hand side is either 0 or imaginary, but
momentum cannot be imaginary so it must be zero

But
2
p x 0 Why ???
SUMMARY
Classical and quantum behaviour of a particle confined in one dimensional Box

Features Classical behaviors Quantum behaviors

1. Allowed A classical particle The particle can have discrete

energy levels have any energy energy values given by
2 2
En 2
n 2 ; n 1,2,3...
2mL
The minimum energy The minimum energy of the
of the particle is zero particle is 2 2
2. Minimum E1
energy 2mL2
It has a value at all The probability of finding the
points within the well quantum mechanical particle at
3. Position
position x depends on I n(x)I2
probability
and hence has different points and
for different states.

22
 Finite Potential Well
Potential energies are never infinite in the real world, and the box
with infinitely hard walls of the previous section has no physical
counterpart.
However, potential wells with barriers of finite height certainly do
exist.
Let us see what the wave functions and energy levels of a particle in
such a well are.

U x 0

U(x) = 0 0 x L

U x L

We also assume that energy of the particle, E, is less than the

“height” of the barrier, i.e. E < U
In regions I and III Schrödinger’s steady-state equation is

The solutions are real exponentials:

Both I and III must be finite everywhere. Since e-ax → as x → -

and eax → as x → , the coefficients D and F must therefore be 0.
Hence we have
These wave functions decrease exponentially inside the barriers at
the sides of the well.
Within the well
2
d 2 II
2
E II
2m d x

In the case of a well with infinitely high barriers, we found that B = 0 in

order that = 0 at x = 0 and x = L. Here, however, II = C at x = 0 and II =
G at x = L, so both the sine and cosine solutions are possible
For either solution, both and d /dx must be continuous at x = 0 and x
= L: the wave functions inside and outside each side of the well must not
only have the same value where they join but also the same slopes, so they
match up perfectly.
When these boundary conditions are taken into account, the result is
that exact matching only occurs for certain specific values En of the particle
energy.
 Wave function and probability

Because the that fit into the well are longer than for an infinite well
of the same width, the corresponding particle momenta are lower (we
recall that = h/p). Hence the energy levels En are lower for each n
than they are for a particle in an infinite well.
Outside the potential well, classical physics forbids the presence of the
particle
Quantum mechanics shows the wave function decays exponentially to zero

The functions are smooth at the boundaries

Outside the box, the probability of finding the particle decreases

exponentially, but it is not zero!
Tunneling
situation of a particle that strikes a potential barrier of height U,
again with E < U, but here the barrier has a finite width

The potential energy has a constant value U in the region of width L

and zero in all other regions. This a called a barrier
When a particle of energy E < U approaches a potential barrier,
according to classical mechanics the particle must be reflected.
In quantum mechanics, the de Broglie waves that correspond to the
particle are partly reflected and partly transmitted, which means
that the particle has a finite chance of penetrating the barrier.

Let us consider a beam of identical particles all of which have the

kinetic energy E. The beam is incident from the left on a potential
barrier of height U and width L.

On both sides of the barrier U = 0, which means that no forces act on

the particles there.
 I+ : incoming particles moving to the right
I- : reflected particles moving to the left;
III : transmitted particles moving to the right.
II : particles inside the barrier, some of which end up in region III while
the others return to region I.
The transmission probability T for a particle to pass through the barrier is
equal to the fraction of the incident beam that gets through the barrier.
Approximate value of probability is given by

L: width of the barrier

• According to quantum mechanics, all regions are accessible
to the particle
– The probability of the particle being in a classically forbidden region
is low, but not zero
– Amplitude of the wave is reduced in the barrier
– A fraction of the beam penetrates the barrier

The examples of tunnel effect:

Alpha particles emitted by certain radioactive nuclei. An alpha
particle whose K.E is only a few MeV is able to escape from a nucleus
whose potential wall is perhaps 25 MeV high.
The probability of escape is so small that the alpha particle might
have to strike the wall 1038 or more times before it emerges, but
sooner or later it does get out.
Operation of certain semiconductor diodes in which e- pass
through potential barriers even though their K.E < U
Scanning Tunnelling Microscope (STM)
Based on principle:
Atomic Force Microscope (AFM)
 Simple Harmonic Oscillator(SHO)
Harmonic Motion:
Vibrates about an equilibrium configuration

Condition: presence of restoring force that acts to return

the system to its equilibrium position when it is disturbed

For SHM:

Classical treatment : Hooks law

solution
Any system in which something executes small vibration about an
equilibrium positions behaves like SHO
Potential energy U is related to F :

WHY TO STUDY:
This approach indentifies several problems:
1. diatomic molecule
2. an atom in a crystal lattice etc
3. explain blackbody radiation;

Energy Levels:
Schrödinger equation for SHO

Introducing dimensionless quantities

In terms of y and , Schrödinger equation becomes

The solutions to this equation that are acceptable here are limited by the
condition that → 0 as y → in order that

Otherwise the wave function cannot represent an actual particle.

The mathematical properties of this Eq. are such that this condition will be
fulfilled only when

Energy level of H.O.

Zero point Energy

H.O. in equilibrium with its surroundings would approach an energy
of E = E0 and not E = 0 as the temperature approaches 0K.
 a particle in a box a harmonic oscillator. a hydrogen atom

Wave Functions
For each choice of the parameter n there is a different wave function n.

Each function consists of a polynomial Hn(y) (Hermite polynomial)

in either odd or even powers of y, the exponential factor e-y2/2, and
a numerical coefficient which is needed for n to meet the
normalization condition

The general Formula of wave functions:

Classical oscillator: The probability P of finding the particle at a given position is
greatest at the endpoints of its motion, where it moves slowly, and least near the
equilibrium position (x = 0), where it moves rapidly.
Quantum Oscillator: The probability density has its maximum value at x = 0 and
drops off on either side of this position. However, this disagreement becomes less
and less marked with increasing n
In more detail:
• Decaying wavefunction tunnels into classically forbidden region
• Spatial average for high energy wavefunction gives classical result:
another example of the CORRESPONDENCE PRINCIPLE

1
E nh h
2
Term ½hν tells us that quantum SHO always oscillates. These are
called zero point vibrations

The zero point energy ½hν is required by the Heisenberg uncertainty

relationship

this qualitative explains why helium does not become solid under normal
conditions: the “zero point vibration” energy is higher than the “melting
energy” of helium

Force between two metal plates

Examples:

Change x to y then finally change y to x

 Assignments-VI Due date 18th Nov 2015

1. Normalise the wave function ( x) A exp ax 2 , A and a are constants, over the
domain - x + .

2. The wave function of a particle of mass m moving in a potential V(x) is

km
( x, t ) A exp ikt x2

, where A and K are constants. Find the explicit form of the potential V(x).

3. A and B are two operators defined by A (x) = (x) + x and B (x) = (d /dx) + 2 (x).
Check for their linearity.

4. Find the value of the operator product

d d
(i ) x x
dx dx
d d
(ii ) x x
dx dx
Thank you...
&

BEST OF LUCK