Quantum Mechanics

1
 Schr dinger’s cat paradox
Ö
(connect microscopic world with macroscopic world and make observation)

A cat, a flask of poison, and a radioactive source are placed in a sealed box. If an internal monitor
(e.g. Geiger counter) detects radioactivity (i.e. a single atom decaying), the flask is shattered, releasing
the poison, which kills the cat.

The Copenhagen interpretation of quantum mechanics implies that after a while, the cat
is simultaneously alive and dead.

N = N0 e-λt
Yet, when one looks in the box, one sees the cat either alive or dead not both alive and dead.
This poses the question of when exactly quantum superposition ends and reality collapses into
one possibility or the other.
 Wavefunction :
the variable quantity characterizing the de Broglie waves is the Wavefunction

What does ψ(x, t) tell us?

Phase of (x,t) is not observable

The probability of finding a particle in the range x to x+dx at
time t is proportional to |(x,t)|2 dx

Born interpretation

 P( x ) dx = 1 (one particle!)
−
Basic postulates of Quantum mechanics
Probabilities in QM are determined
from wave functions (not observable)

Complex Wavefunction
2
Observable
Well behaved
 must be continuous and single-valued everywhere
/x must be continuous and single-valued everywhere
 must go to zero as x → ± 
Probability of finding the particle between
 Superposition
If 1 and 2 are two wavefunctions that satisfy the
equation, then any linear combinations of 1 and 2 is
also a solution

where a and b are constants.

 Position probabilities with a discrete wavefunction

• How do we use  to predict the results of a measurement of the particle's

position?

• A simple case
Suppose a particle can exist in only three points: x=1, x=2, and x=3.
Our particle must be on exactly one of those points. It cannot be
anywhere else, including in between them.
So  is just three complex numbers, which might look something like
this.
x = 1:  = 1 + i
x = 2:  = 2 - 2i
x = 3:  = 2 + 2i
• ||2 gives the probability of finding the particle at a particular
position.

• The probability of finding our particle at position x=1 is *,

which is 2.

The probability at the position x=2 is 8.

So, for any given measurement, we are four times as likely to find
the particle at position 2 as at position 1.

• Similarly, the probability at position x=3 is 8

• Now, if we sum up the probabilities of all three locations, we get

the odds that the particle will be in any one of those three states.
Since we've already said that the particle must be at one of those
states, we should get a total probability of 1.
• But at the moment, we find a total probability of 18!

• This wavefunction is unnormalized:

• It can tell us the relative probabilities of two positions, but not the
absolute probabilities of any of them.

• To normalize it, we multiply all the values by a constant, to make

the total probability equal to 1.

• In this case, we have to multiply every value of ||2 by 1/18, which

means we multiply every value of  by the square root of 1/18.
This will keep all the relative probabilities the same, but ensure
that the total probability of finding the particle somewhere is 1.
• So now, at our three places, we have the
following.
x=1, probability=2/18
x=2, probability=8/18
x=3, probability=8/18

• That is a properly normalized description of the

particle's position. You can't say for sure what any
given measurement will find, but you know
exactly what the odds are.
Therefore the wave-functions at the three places can be
written as:

probability=2/18

probability=8/18

probability=8/18
• “Expectation value" of position

Expectation value < x > of the position of a particle described

by wave function (x,t), is the value of x we would obtain if
we measured the position of a large number of particles
described by the same wavefunction at some instant t and then
averaged the results.

It is not the most probable value of a measurement.

 For a large number of identical particles, distributed along x-axis
so that there are N1 particles at x1, N2 at x2 etc…:

The average position of the identical particles:

x=
N1 x1 + N 2 x2 + N 3 x3 + ...
=
N x
i i

N1 + N 2 + N 3 + ... N i

If we deal with single particle, we must replace Ni of particles at xi by

the probability Pi, that the particle be found in interval dx at xi.
2
Pi = i dx

where i is the particle wave-function at x=xi.

 x=
 Nx i i

N i

Expectation value of the position of a single particle is:



x
2
dx
x = −



2
 dx
−
If  is normalised wave function,



2
x = x  dx
−
Note that <x2> ≠ <x>2
Prove for  = Csin(πx)/L
Problem: A particle limited to the x-axis has the wave function  = ax
between x = 0 and x = 1;  = 0 elsewhere.
(a) Find the probability that the particle can be found between x = 0.45
and x = 0.55.
(b) Find the expectation value <x> of the particle’s position.
Solution:
(a) The probability is:
x2 0.55 0.55
3
x
  dx = a  x dx = a
2 2 2 2
= 0.0251a 2
x1 0.45
3 0.45

(b) The expectation value is:

1 1 1
4 2
x a
x =  x  dx = a  x dx = a
2 2 3 2
=
0 0
4 0
4
Consider a particle moving in one dimension. De Broglie hypotheis –
associated with a free particle, there is a harmonic wave.
Ψ(x,t) = A[cos (kx-ωt) + i.sin(kx-ωt)]

i ( kx −t )
Wave function:  ( x, t ) = Ae
E = hυ E = ħ and
λ = h/p p = ħk
i
( px − Et )
 ( x, t ) = Ae 
 i
( px − Et )
 ( x, t ) = Ae 
Successive differentiation will give


i = E ( x , t )
t

− i = p ( x , t )
x


Momentum operator: pˆ x  − i
x

ˆ 
Energy operator: E  i
t
 Schrödinger’s equation

Momentum operator: pˆ x  − i
x

Total energy operator: Eˆ  i 
t
Now the total energy of a particle is just the sum of the kinetic energy and the potential
energy:

E = p2/2m +V
 1 2  
2
In “operator” form this i = (− i ) 2 + V
becomes: t 2m x

Rearranging we get  2  2 
Schrödinger’s equation: − + V  = i 
(one dimensional version) 2m  x 2 t
Things to note from Schrödinger’s eqn.
 2  2 
− + V  = i 
2m  x 2 t
Differences between Schrödinger and classical wave equations
 2  2   2y 1  2y
− + V  = i  = 2
2m  x 2 t  x 2
v  t2
K.E. + P.E. = Total
Energy

Schrödinger Wave Equation Classical Wave Equation

Eqn. derived from total energy Eqn. derived from force
First order derivative w.r.t. time Second order derivative w.r.t time
Complex Equation Real Equation
➔ y is a displacement : Real
For a free particle, V=0. Therefore, we have
    ( x, t )
2 2
i =−
t 2m x 2

This is the one-dimensional time dependent Schrödinger

equation for a free particle.

We also get that E and p can be represented by: i = E ( x , t )
t

− i = p ( x , t )
x

 
E → i p → −i
t x
The particle to be in a field characterized by the potential energy
function V(x,t) then according to classical mechanics, the total energy
would be given by:
E= p2/2m + V(x,t)

Since the potential energy function does not depend on p and E, we

have from preceeding two important equations that the wave-function
should satisfy

Where H= p2/2m + V and is known as the

Hamiltonian.
 Shrödinger Equation

For conservative systems having time-independent potential energy V(x):

Separation of variables
  2 1  2 ( x ) 1
− + V ( x) = H ( x ) = E
2 m  ( x ) x 2
 ( x)
Time independent Schrödinger eqn.
 iEt
−
f (t ) = Ce 
 iEt
−
 ( x, t ) = C ( x )e 

iEn t
−
n ( x, t ) = Cn n ( x)e 

Note that t in the above equation is only a phase factor.

It does not effect the probability distribution or expectation value.

As t does not appear in the measurable quantities the eigenstates

of the time-dependent Schrödinger equation of a conservative
system are known as the stationary states.
Time dependent form of Schrödinger eqn.

Time independent Schrödinger eqn. :

Example: One dimensional Potential well
~ particle in a box
V0 Infinite
L

-V0 V(x)= 0 for 0<x<L

=∞ for x<0 and for x>L
 Particle in a box
Region I Region II Region III

Time Independent Schrödinger

V(x)=∞ V(x)=0 V(x)=∞
Equation : 1-dimensional

−  2 d 2 ( x )
2
+ V ( x ) = E
0 L x 2m dx
V(x)=0 for L>x>0
V(x)=∞ for x≥L, x≤0
Applying boundary conditions:
Classical Physics: The particle can
exist anywhere in the box and follow a Region I and III:
path in accordance to Newton’s Laws.
−  2 d 2 ( x )
+  * = E  =0
2
Quantum Physics: The particle is 2m dx 2

expressed by a wave function and there Region II:

are certain areas more likely to contain −  2 d 2 ( x )
the particle within the box. 2
= E
2m dx
 Wave Function : Time Independent Solution

−  2 d 2 ( x ) d 2 ( x ) 2m
Our new wave function:
= E − = 2 E nx
2m dx 2 dx 2   II = A sin But what is ‘A’?
L
This is similar to the general differential equation:
Normalizing wave function:
L
d 2 ( x )  = A sin kx + B cos kx  dx = 1
2
− 2
= k 2 ( A sin kx )
dx 0
So we can start applying boundary conditions: L
x=0 ψ=0  x sin 2kx 
2
0 = A sin 0k + B cos 0k 0 = 0 + B *1 B = 0 A  −  =1
 2 4 k 0
x=L ψ=0 n=1,2,3… n 
0 = Asin kL 
A0 kL = n sin 2 L
n≠0 2L L
A  − =1
2 n 
Calculating Energy Levels:  4 
 L 
2 mE k 2 2 k 2h2
k = 2
2
E= E=
 2m 2m 4 2 2 L  2
h A   =1 A=
= 2 L
2
Our normalized wave function is:
n
2 2
h 2
2 2
E= n h nx
L 2m 4 2
2
E=  II =
2
sin
8mL2 L L
 Particle in a 1-Dimensional Box

nx nx 
2
2 Applying the 2
 II =  II
2
sin Born Interpretation =  sin 
L L L L 

n=4 n=4

E n=3 E n=3

n=2 n=2

n=1 n=1

x/L x/L
 Standing de Broglie waves

Eg electron in a “box” (infinite potential well)

V= V= V= V=

V=0 V=0

Electron “rattles” to and fro Standing wave formed

wavelengths of confined states

In general, k =nπ/L,
n= number of antinodes in
standing wave

2L 3
= ;k =
3 L
2
 = L;k =
L

 = 2L ; k =
L
 Kinetic Energy of particle

2 2 2 2
p h  k
KE = = =
2 m 2 m 2
2m

If the de Broglie hypothesis is correct, then a stream of

classical particles should show evidence of wave-like
characteristics……………………………………………
energies of confined states

2
 k  n 
2 2 2 2
E= = 2
2m 2mL

En = n E1
2

 2 2
E1 =
2mL2
Energies of confined states

En = n E1
2 2 2
E1 =
2mL2
 particle in a box: wave functions

From our previous lecture, standing wave on a string has form:

y ( x, t ) = ( A sin kx ) sin(t )

Our particle in a box wave functions represent STATIONARY

(time independent) states, so we write:

 ( x) = A sin kx

A is a constant, to be determined……………
normalisation of wave functions

 nx 
L L

  ( x) A  sin 
2
dx = 1  dx = 1
2 2

0 0  L 

2 nx
 ( x) = sin
L L
The complete time-dependent wave function
for particle in a box:

nx
iE n t iE n t
− 2 −
n ( x, t ) =  n ( x )e 
= sin e 
L L
Find the probability that a particle
trapped in one dimensional box of length
L can be found between 0.45L and 0.55L
for the ground state.
 Tunable Optical Properties
II-VI Semiconductor : Quantum size effect

CdS and CdSe : Tunability of optical absorption/emission in the

whole visible spectrum

Talapin et al., Nano Lett., 3,1677 (2003)

 Nanoparticles / Quantum Dots
Absorption and emission occur at specific wavelengths,
which are related to QD size

Eg

Nanohub.org @ Univ. of Pennsylvenia

 GaN : Blue LED for White Light

Physics Nobel Prize 2014

Akasaki Amano Nakamura

InGaN quantum wells

in GaN : Blue LED +
Yellow Phosphor
 Electron trapped inside the atom
-10 Ground state energy
L=10 m
 Ground state energy

-15
L=2x10 m
 Infinite Potential Well
2  n 
 n ( x) = sin  x ; (0  x  L )
L  L 
L

-V0
 Finite depth well
V0 Finite
L

-V0
 Quantum Well with Finite Potential

Wavefunctions Probability densities

We have exponential wavefunctions outside the box
I = A eCx and III = B e-Cx
and sinusoidal wavefunctions inside the box.
 II = F sin (kx) + G cos (kx)
 One dimensional Potential step

E > V0
V0

E < V0

x
 One dimensional Potential barrier
Quantum mechanical tunneling
T = C.exp(-2bL) with b = (2m(V0-E)/ħ2)1/2

E < V0 V0 L : barrier width

x
More the barrier height less the transmission probability
More the barrier width less the transmission probability
 Scanning Tunnel Microscope (STM)
- Application of quantum
mechanical tunneling:
A conducting very sharp tip (< 1nm) is
positioned very close to the surface of a
specimen (about a nanometer).

•When the tip is very close to the electron

cloud around the surface atoms in the
specimen, electrons will tunnel through the
barrier with an exponential probability with
surface/tip distance T =Ce-2bL
A schematic diagram of a
scanning tunnel microscope.
 Atomic Resolution STM image of Graphite

Each of the yellowish dots in the highlighted, magnified

area represents one of the atoms which form the typical
hexagonal “honeycomb” structure of the graphite lattice.
public/news/blog/2006-2009/2009-01-23_atomic-resolution-stm.txt- Last modified:
2017/01/04 19:58 by schniepp
Resonant Tunneling Diode (RTD)
Tunnel diode : Quantum tunneling in a P-N junction
Linear Harmonic oscillator

Zero-point
energy
 2

2
2

2
 Harmonic Oscillator

Wavefunction Probability density

Source: https://commons.wikimedia.org
 Remarks
Characteristic quantum properties are manifest everywhere:
• Colour of objects
• Energy bands in solids
• Mechanical, chemical and electrical properties of different
substances
• Electronics, magnetism
• Nuclear processes
• Quantum Technology : Devices, Metrology, Secure
communication, Computation

“Although an unambiguous description of atomic reality is impossible

with our ordinary concepts of material processes, we have an
unambiguous mathematical scheme (QUANTUM MECHANICS)
that gives the right predictions and probabilities for any observation.”