Quantum Mech.

Basics:
Lecture-1
DBroglies wave particle duality and relation
Particle in a box with infinite potential walls.
Wave Function and its meaning
Time independent Schrodingers Equation
Quantum Dots & Particle in a Box.
Wave-Function: Properties and Details
Lecture-2
Finite Potential well
Molecular beam Epitaxy
Tunneling across finite potential barrier
Scanning Tunneling Microscope.
Flash Memory

Lecture-3 (Optional as already covered in Y1 Phy-Chem)

Understand importance of Schrodingers equation w.r.t. ATOM.
Understand the probability distribution (Radial & Angular)
Shapes of orbitals
Paulis exclusion principle
 LECTURE-1
DBroglies wave particle duality and relation
Particle in a box with infinite potential walls.
Wave Function and its meaning
Time independent Schrodingers Equation
Quantum Dots & Particle in a Box.
Wave Function: Properties & details
 The de Broglie Hypothesis
In 1924, de Broglie suggested that if waves of wavelength
were associated with particles of momentum p=h/,
then it should also work the other way round.

A particle of mass m, moving with velocity v has

momentum p given by:

h
p mv

 Kinetic Energy of particle

2 2 2 2
p h k
KE
2m 2m 2
2m

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

classical particles should show evidence of wave-like
characteristics
 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 =n/L, n= number of

antinodes in standing wave

2L 3
;k
3 L
2
L;k
L

2L ; k
L
Energies of confined states

k2
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

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
 Interpretation of the wave function

The wave function of a particle is related to the probability

density for finding the particle in a given region of space:

Probability of finding particle between x and x + dx:

( x) dx
2

Probability of finding particle somewhere = 1, so we have

the NORMALISATION CONDITION for the wave
function:

( x) dx 1
2

Interpretation of the wave function
 Interpretation of the wave function
Normalisation condition allows unknown constants in the
wave function to be determined. For our particle in a box
we have WF:

nx
( x) A sin kx A sin
L
Since, in this case the particle is confined by INFINITE
potential barriers, we know particle must be located
between x=0 and x=L Normalisation condition reduces
to :
L

( x) dx 1
2

0
Particle in a box: normalisation of wave functions

nx
L L

( x) dx 1 A sin dx 1
2 2 2

0 0 L

2 nx
( x) sin
L L
 Some points to note..

So far we have only treated a very simple one-dimensional

case of a particle in a completely confining potential.

In general, we should be able to determine wave functions

for a particle in all three dimensions and for potential
energies of any value

Requires the development of a more sophisticated

QUANTUM MECHANICS based on the SCHRDINGER
EQUATION
 Schrodinger: A Wave Equation for Electrons

Schrodinger guessed that there was some wave-like quantity

that could be related to energy and momentum

wavefunction
Schrodinger: A Wave Equation for Electrons

(free-particle)

(free-particle)

..The Free-Particle Schrodinger Wave Equation !

Erwin Schrdinger (18871961)

Image in the Public Domain
 Schrodinger Equation and Energy Conservation
... The Schrodinger Wave Equation !

Total E term K.E. term P.E. term

... In physics notation and in 3-D this is how it looks:

Electron
Maximum height Potential
and zero speed Energy
Zero speed start

Incoming
Electron

Fastest Battery
 Time-Dependent Schrodinger Wave Equation

Total E K.E. term P.E. term

PHYSICS term
NOTATION

Time-Independent Schrodinger Wave Equation

 Particle in a Box

e-

0.1 nm

The particle the box is bound within certain regions of space.

If bound, can the particle still be described as a wave ?
YES as a standing wave
(wave that does not change its with time)
A point mass m constrained to move on an infinitely-thin,
frictionless wire which is strung tightly between two
impenetrable walls a distance L apart

0
L

WE WILL HAVE MULTIPLE SOLUTIONS FOR ,

SO WE INTRODUCE LABEL

IS CONTINUOUS
 WE WILL HAVE e-
MULTIPLE SOLUTIONS
FOR ,
SO WE INTRODUCE
LABEL n
L

REWRITE AS:

WHERE

GENERAL SOLUTION:

OR
USE BOUNDARY CONDITIONS TO DETERMINE COEFFICIENTS A and B

e-
since

NORMALIZE THE INTEGRAL OF PROBABILITY TO 1

L
EIGENENERGIES for EIGENSTATES for PROBABILITY
1-D BOX 1-D BOX DENSITIES
Quantum Confinement
another way to know x
Quantum dot

insulator

+e +e +e
r

electron can be anywhere in the dot

Semiconductor Nanoparticles
(aka: Quantum Dots)
Core Shell
Core
Quantum
Dot

Determining QD energy
using the Uncertainty Principle
Red: bigger dots!
Blue: smaller dots!
 Semiconductor Nanoparticles
(aka: Quantum Dots)
Determining QD energy
Core Shell
using the Schrdinger Equation
Core
Quantum
Dot

Red: bigger dots!

Blue: smaller dots!

Photo by J. Halpert LBLUE QD LRED QD

Courtesy of M. Bawendi Group, Chemistry, MIT
 The Wavefunction: Properties and Details
corresponds to a physically meaningful quantity
- the probability of finding the particle near x
is related to the momentum probability density -
- the probability of finding a particle with a particular momentum

PHYSICALLY MEANINGFUL STATES MUST HAVE THE FOLLOWING PROPERTIES:

(x) must be single-valued, and finite

(finite to avoid infinite probability density)

(x) must be continuous, with finite d/dx

(because d/dx is related to the momentum density)

In regions with finite potential, d/dx must be continuous

(with finite d2/dx2, to avoid infinite energies)

There is usually no significance to the overall sign of (x)

(it goes away when we take the absolute square)
(In fact, (x,t) is usually complex !)
 Physically Meaningful Wavefunctions
1. Which of the following hypothetical wavefunctions is acceptable for a particle in
some realistic potential V(x)?

(x) (x) (x)

(a) (b) (c)

x x x

2. Which of the following wavefunctions corresponds to a particle more likely to be

found on the left side?

(a) (b) (c)

(x) (x) (x)

0 x 0 x 0 x
 Schrodinger Equation and Energy Conservation

Notice that if V(x) = constant, this equation has the simple form:

where is a constant that might be positive or negative.

For positive C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax

For negative C, what is the form of the solution?

a) sin kx b) cos kx c) eax d) e-ax

 Solutions to Schrodingers Equation

The kinetic energy of the electron is related to the

curvature of the wavefunction

Tighter confinement Higher energy

Even the lowest energy bound state requires some wavefunction
curvature (kinetic energy) to satisfy boundary conditions..

Nodes in wavefunction Higher energy

The n-th wavefunction (eigenstate) has (n-1) zero-crossings
 Sketching Solutions to Schrodingers Equation

Estimate the wavefunction for an electron in the 5th energy level of this
potential, without solving the Schrodinger Eq. Qualitatively sketch the 5th
wavefunction:

Things to consider:
V= V=
(1) 5th wavefunction has ___ zero-crossings
zero-crossings.
E5
(2) Wavefunction must go to zero at x = _0 and
Vo x = _.
L.

0 x (3) Kinetic
Kineticenergy
energyisis ______
____ ononright
rightside
sideofofwell,
well,
L
so the curvature
so the of ofis_____
curvature there
is _____ (wavelength
there

is longer).
(wavelength is longer).

(4) Because kinetic energy is ______ on right side

x of the well, the amplitude is _______ .
 WHICH WAVEFUNCTION CORRESPONDS TO WHICH POTENTIAL WELL ?

(A)

(1)

(B)

(2)

(C)

(3)

NOTICE THAT FOR FINITE POTENTIAL WELLS WAVEFUNCTIONS ARE NOT ZERO AT THE WELL BOUNDARY
 LECTURE-2
Finite Potential well
Molecular beam Epitaxy
Tunneling across finite potential barrier
Scanning Tunneling Microscope.
Flash Memory
Solving the Schrodinger equation allows us to calculate
particle wave functions for a wide range of situations.

Finite potential well

WF leakage, particle has finite probability of being found in barrier:

CLASSICALLY FORBIDDEN
Molecular Beam Epitaxy: Man-made potential wells for
Quantum mechanical engineering
Molecular Beam Epitaxy: Man-made potential wells for
Quantum mechanical engineering
 A Simple
Potential Step

CASE I : Eo > V

Region 1 Region 2

In Region 1:

In Region 2:
A Simple
Potential Step

CASE I : Eo > V

Region 1 Region 2

is continuous:

is continuous:
A Simple
Potential Step

CASE I : Eo > V

Region 1 Region 2
Example from: http://phet.colorado.edu/en/get-phet/one-at-a-time
 Quantum Electron Currents

Given an electron of mass

that is located in space with charge density

and moving with momentum corresponding to

then the current density for a single electron is given by

A Simple
Potential Step

CASE I : Eo > V

Region 1 Region 2
A Simple
Potential Step

CASE I : Eo > V

Region 1 Region 2

1
 A Simple
Potential Step

CASE II : Eo < V

Region 1 Region 2

In Region 1:

In Region 2:
A Simple
Potential Step

CASE II : Eo < V

Region 1 Region 2

is continuous:

is continuous:
 A Simple
Potential Step

CASE II : Eo < V

Region 1 Region 2

Total reflection Transmission must be zero

Quantum Tunneling Through a Thin Potential Barrier

Total Reflection at Boundary

Frustrated Total Reflection (Tunneling)

KEY TAKEAWAYS CASE I : Eo > V

A Simple Potential Step

Region Region
1 2

PARTIAL REFLECTION

CASE II : Eo < V

Region Region
1 2

TOTAL REFLECTION
Solving the Schrodinger equation allows us to calculate
particle wave functions for a wide range of situations.

Barrier Penetration (Tunnelling)

Quantum mechanics allows particles to travel through brick walls!!!!

A Rectangular
Potential Step

CASE II : Eo < V

Region 1 Region 2 Region 3

In Regions 1 and 3:

In Region 2:

for Eo < V :
A Rectangular
Potential Step

for Eo < V :
 Example: Barrier Tunneling
Lets consider a tunneling problem:
An electron with a total energy of Eo= 6 eV
V0
approaches a potential barrier with a height of
Eo
V0 = 12 eV. If the width of the barrier is
metal metal
L = 0.18 nm, what is the probability that the
0 L air x
electron will tunnel through the barrier?
gap

Question: What will T be if we double the width of the gap?

 Multiple Choice Questions
Consider a particle tunneling through a barrier:

1. Which of the following will increase the V

likelihood of tunneling? Eo

a. decrease the height of the barrier 0 L x

b. decrease the width of the barrier
c. decrease the mass of the particle

2. What is the energy of the particles that have successfully escaped?

a. < initial energy
b. = initial energy
c. > initial energy
Although the amplitude of the wave is smaller after the barrier, no
energy is lost in the tunneling process
 Application of Tunneling:
Scanning Tunneling Microscopy (STM)
Due to the quantum effect of barrier penetration, the
electron density of a material extends beyond its surface:

One can exploit this material STM tip

to measure the
~ 1 nm
electron density on a
materials surface: material
STM tip
Sodium atoms
on metal:
E0 V

Single walled
carbon nanotube:
STM images
Image originally created
by IBM Corporation

IBM Corporation. All rights reserved. This content is excluded from our Creative
Commons license. For more information, see http://ocw.mit.edu/fairuse. Image is in the public domain
Scanning Tunnelling Microscope: Imaging atoms
 1981 Invention of Scanning Tunneling Microscopy
 G. Binning, H. Rohrer, C. Berger and E. Weibel
Surface studies by Scanning Tunneling Microscopy,
Phys. Rev. Lett. 49, 57-61 (1982)

1986 First International Conference on STM

Santiago de Compostela, Spain, 14-18 July

1986 Nobel Prize to G. Binning and H. Rohrer

1988 STM Imaging of DNA and biological structures

 IBM Almaden STM of Copper

Image originally created by the IBM Corporation.

IBM Corporation. All rights reserved. This content is excluded from our Creative Commons
license. For more information, see http://ocw.mit.edu/fairuse.
 IBM Almaden
Image originally created by the IBM Corporation.
IBM Corporation. All rights reserved. This content is excluded from our Creative Commons
license. For more information, see http://ocw.mit.edu/fairuse.
 IBM Almaden
Image originally created by the IBM Corporation.
IBM Corporation. All rights reserved. This content is excluded from our Creative Commons
license. For more information, see http://ocw.mit.edu/fairuse.
 Flash Memory
Stored
Electrons

Erased Programmed
1 0

Image is in the public domain

CONTROL GATE Insulating

Floating
Dielectric
Tunnel Oxide Gate
FLOATING GATE

SOURCE DRAIN
CHANNEL
Channel

Substrate

Electrons tunnel preferentially when a voltage is applied

 MOSFET: Transistor in a Nutshell
Conduction electron flow

Control Gate

Conducting Channel
Semiconductor
Image courtesy of J. Hoyt Group, EECS, MIT.
Photo by L. Gomez
Image courtesy of J. Hoyt Group, EECS, MIT.
Photo by L. Gomez

Tunneling causes thin insulating layers

to become leaky !
Image is in the public domain
 Reading Flash Memory

UNPROGRAMMED PROGRAMMED

CONTROL GATE CONTROL GATE

FLOATING GATE FLOATING GATE

SILICON

To obtain the same channel charge, the programmed gate needs a

higher control-gate voltage than the unprogrammed gate

How do we WRITE Flash Memory ?

 LECTURE-3
(Optional as already covered in Y1 Phy-Chem)
 Schrdinger equation

Gave an equation for find our the wave

function of any system.
Solution to WAVE EQUATION gives set
of mathematical expressions called
WAVE FUNCTIONS, Y
E. Schrodinger Each describes an allowed energy state of
1933 Nobel an e-
Quantization introduced naturally.

Paper of Schrodinger
Schrodingers equation.(Quantum numbers)

Origin of the Schrodingers equation

Video

Through above equation you get Psi

If V=0
Max Borns Interpretation
Star watchers

69
Wave functions Corresponding to radial and angular parts

70
Solutions to Wave functions corresponding to radial and angular parts

71
Probability density (radial) of electrons around the nucleus

72
Probability distribution (radial) of electrons around the nucleus

http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/hydwf.html#c1
Probability distribution (radial) of electrons around the nucleus

74
Shapes of atomic orbitals.
Probability distribution (angular) of electrons around the nucleus

77
Shapes of atomic orbitals.
Radial Probability density and Bohr radius

09-10-2014
Shape of electron cloud

09-10-2014
Jump of electron from one shell to another

09-10-2014
Schrodinger equation for many electron system and Paulis exclusion principle.

https://www.youtube.com/watch?v=I93gZ_zfOpg