CH103 Part 1

Physical Chemistry: y y
Introduction to Bonding
From Quantum Mechanics to
At i d M l l St t Atomic and Molecular Structure
I t t P f A i d Ch dh Instructor: Prof. Arindam Chowdhury,
Department of Chemistry, Room 215
Phone: 2576-7154 Email: arindam@chem.iitb.ac.in
Contents in Physical Chemistry (10 Lectures):
Introduction and Motivations to learn Physical Chemistry Today
Schrodinger Equation (Origin or Quantization): Lecture 1-3
Failures of Classical Mechanics Failures of Classical Mechanics
Postulates of Quantum Mechanics
Example of Energy Quantization: Particle in a 1-D Potential Well
Atomic Structure: Lecture 4-6
Hydrogen Atom and Quantum Numbers
Atomic Orbitals and Electron Densities
M lti l t t Multi-electron atoms
Chemical Bonding: Lectures 7-9
Molecular Orbital Theory Molecular Orbital Theory
Energy Levels of Diatomic Molecules
Molecular Structure: Lecture 10
Bonding in Polyatomics using Hybridization
Recommended Text (Physical)
Physical Chemistry I.N. Levine, 5
th
Ed.
Physical Chemistry P.W. Atkins 2
nd
Ed.
Physical Chemistry: A Molecular Approach McQuarrie and Simon Physical Chemistry: A Molecular Approach - McQuarrie and Simon
Websites:
wwwchemiitb ac in/academics/menu php www.chem.iitb.ac.in/academics/menu.php
(CH103 Course Material for 2008 and 2009); ,
IITB-Moodle http://moodle.iitb.ac.in p
http://www.falstad.com/mathphysics.html#qm
http://www.meta-synthesis.com/webbook.html
http://ocw.mit.edu/OcwWeb/web/courses/courses/index.htm#Chemistry
http://education.jimmyr.com/Berkeley_Chemistry_Courses_23_2008.php
Why should we study Chemistry?
Is there a role of Chemistry in
h i th d ld? reshaping the modern world?
All of Science and Engineering is moving towards
interdisciplinary fields of cutting edge research!!! interdisciplinary fields of cutting-edge research!!!
Knowing only one subject often not good enough!
Chemistry has a major role to play
1. Nanoelectronics/Nanotechnology: Molecular Electronics
2. Energy Science Solar Energy conversion
3. BioTechnology Disease cure, health, medicine: Playing God
4. Atmospheric Science Have to Save the World
Plastic Electronics and Displays
Conducting-polymers are replacing standard liquid crystals
Organic Light Emitting Diodes
LEDs from Conducting Polymers: MEH-PPV
Macro, Micro & Nano-electronics
1947, Transistor, Bell Labs
Silicon Transistor, TI 1954
Intel, 1990s, hundreds of
Transistors in a single chip
Transistors, Intel, 2006, 45 nm separation
Next Generation: Molecular Chips
Nano-Wires and Molecular Electronic Devices
The Goal of Molecular Electronics
Solar Energy Conversion
Solar energy conversion with high efficiency has been a challenge!
In contract, Nature converts ~80-90% of the light to chemical energy (Photosynthesis)
Seeing Molecules and Surfaces
i h AFM d STM with AFM and STM
It started with Quantum Mechanics
Nano-science
A d N t h l
Mult-electron Atoms
(Periodic Table)
El t At i /M l l And Nanotechnology Electron
Microscopy
Multi-atomic
Bonding, Molecular
Atomic/Molecular
Spectroscopy
Intermolecular Forces
g
Structure
Biology,
Materials Science
Chemical Reactions
Molecular Dynamics
And Interactions Condensed Matter
Physics
Atomic Structure - History
Plum-Pudding Model
J J Thompson J .J . Thompson
(1856-1940)
Rutherfords Gold Foil Experiment
1871-1937
Rutherford beamed alpha particles (++) through gold foil and detected them as ( ) g g
flashes of light or scintillations on a screen. The gold foil was only 0.00004 cm
thick, meaning on a few hundreds of atoms thick
Planetary model loggerheads with
l i l l i h classical electromagnetic theory
Classical EM theory can not
explain Blackbody Radiation explain Blackbody Radiation
All classical theories
led to the so called
Ultraviolet Catastrophe
Sun, starshot iron rod
Ultraviolet Catastrophe
2
3
8
( ) ;
b
k T c
T d d
c

= =
Theories based on classical physics unable to explain temperature
dependence of emitted radiation (radiant energy density)
c
Max Planck assumed energies of
oscillators are discontinuous oscillators are discontinuous
Energy of the electronic oscillators Energy of the electronic oscillators
were discrete and proportional to were discrete and proportional to
E h
were discrete and proportional to were discrete and proportional to
the integral multiple of the frequencies the integral multiple of the frequencies
E = Energy of electronic oscillators
f f ill ti f l t
Osc
E nh =
3
a
v = frequency of oscillation of electrons
h = Plancks constant = 6.626 x e
-34
joule-sec
Note: h came in as a fitting parameter
/
( )
1
v
bv t
a
T d
e

1858-1947
3
8
( )
h d
T d

( )
( )
3
/
5
/
( )
1
8
( )
B
v
h k T
h k T
T d
c
e
hc d
T d

=
Planck never believed his theory was right, since he was a believer of classical physics
( )
5
/
( )
1
B
hc k T
e

Line Spectra of Atoms
Rydbergs formula:

1854-1919
1 2
2 2
1 2
1 1 1
;
H
R n n
c n n

= = = >


R
H
= 109677.57 cm
-1
Bohrs Phenomenological Model
(or Rutherford-Planck-Bohr Model) (orRutherford Planck Bohr Model)
Electrons rotate in circular orbits around
a central (massive) nucleus, and obeys
the laws of classical mechanics the laws of classical mechanics.
Allowed orbits are those for which the
electrons angular momentum equals an
integral multiple of h/2. i.e. m
e
vr = n h/2
Energy of H-atom can only take certain
discrete values: Stationary States
1885-1962
discrete values: Stationary States
The Atom in a stationary state does
not emit electromagnetic radiation
1885-1962
When an atom makes a transition from
one stationary state of energy E
a
to
another of energy E
b
, it emits or absorbs another of energy E
b
, it emits or absorbs
a photon of light: E
a
E
b
= hv
Bohrs model explains atomic spectra!
4
1
h
4
2 2 2
0
1
.
8
e
n
m e
E
h n
=
n=1,2,3,...
2
(2 )
nh
mvr
r n

=
=

Spectral Transitions: E=hv
4
2 2 2 2
1 1
, 1,2,3,...
8
e
i f
i f
m e
E h n n
h n n

= = =



Explains Rydbergs Formula:
Further details in Tutorials as problems!
Photoelectric Effect
1. Increasing the intensity of the light
increasedthe number of photoelectrons
Photodetectors, Photovoltaics,
Elevator sensor, smoke detectors
Experimental Observations
increased the number of photoelectrons,
but not their maximum kinetic energy!
2. Red light will not cause the ejection of g j
electrons, no matter what the intensity!
3. Weak violet light will eject only a
fewelectrons! But their maximumkinetic few electrons! But their maximum kinetic
energies are greater than those for very
intense light of longer (red) wavelengths
0
( ) E E Sin kx t =
0
2
0
( )
Wave Energy related
toIntensity E
0
to
of
Intensity E
Independent

Einstein showed light can behave like particles

BorrowingPlancks idea that E=hv Einstein further proposed that radiation itself Borrowing Plancks idea that E=hv, Einstein further proposed that radiation itself
existed as small packets of energy (Quanta) now known as PHOTONS
Energy of photon
E h =
gy p
Is freq. dependent
P
E h =
1879 1955
2
1
E hv KE mv = = + = +
1879-1955
Energy to remove e' from surface
2
P M
E hv KE mv
=
= = + = +
0
0
M
KE hv =
Packets of light particles: Photons
Kinetic Energy of ejected electrons should be proportional to the frequency (energy)
of the radiation, rather than on the intensities. Intensity of light will increase the
number of electrons, but will saturate once all the electrons are ejected from surface.
Different metals have different work functions (electron binding energies)
Einsteins explanation of Photoelectric Effect
showed the particle nature of light/EM Radiation
Further details in Tutorials as problems!
Light is EM Radiation: Waves
( )
( )
m
m
E E Sin kx t
B B Sin kx t

=
=
10
~3 10 /sec
m
m
E
c cm
B
=
Diffraction/Interference Pattern and Polarization properties show light is a wave
De Broglie Hypothesis: Matter Waves
Si N t lik t it i lik l th t ti l l h ld h lik t
h h
= =
Since Nature likes symmetry, it is likely that particles also should have wavelike nature
p mv

Wave-Packet
1892-1987
of an electron-wave moving @ 10
6
m/s
-34
10
-31
6.6x10 J s
7 10
9.1x10 Kg 1x106 m/s
h
m
mv

= = =

Motion of a Wave-Packet
Further details in Tutorials as problems!
INSIGNIFICANT FOR MACROSCOPIC OBJECTS
Electrons are particles with a
i l i h single negative charge
Essentially how a CRT
Monitor or standard TV
works
J .J . Thompson, Nobel Prize in 1906
works
Electron also show interference
patterns like light: Waves patterns like light: Waves
Davisson and Germer 1927
J .J s son, George Thompson, Nobel Prize 1937
Wave-Particle Duality
Light can be Particles or Waves
Electron/matter can be Particles or Waves
Electrons or photons show both wave and particle
Nature WAVICLE: Best suited to be called a form of Energy
Uncertainty Principle - Heisenberg
h = 6.626 x 10
-34
J s
1901-1976
. ; and .
4 4
x
h h
x p E t


IMPORTANT FOR (FAST MOVING) MICROSCOPIC SYSTEMS
Further details in Tutorials as problems!
Uncertainty Principle: X.P
x
~h/4
Wave-Packet
Specifying position accurately would require many
waves, each having a fixed value of momentum (k), waves, each having a fixed value of momentum (k),
P becomes Completely uncertain.
If only one wave with known k (momentum),
the position becomes completel ncertain the position becomes completely uncertain,
since 1 wave spreads indefinitely in space.
The nature of the world within the submicroscopic
atoms is not directly observable
we deduce it on the basis of highly indirect we deduce it on the basis of highly indirect
evidence, and then proceed to describe it
in terms/quantities which we invented on the in terms/quantities which we invented on the
basis of experience of the macroscopic world.
Classical quantities such as position and
momentum have decreased suitability for y
describing the physics of the subatomic world.