CH103 Part 1

Physical Chemistry:
Introduction to Bonding
From Quantum Mechanics to
Atomic and Molecular Structure
Instructor: Prof. ArindamChowdhury,
Department of Chemistry, Room 215
Phone: 2576-7154 Email: achowdhury(at)iitb.ac.in
arindam(at)chem.iitb.ac.in
Contents in Physical Chemistry (10 Lectures)
Schrodinger Equation (Origin or Quantization): Lecture 1-3
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
Multi-electron atoms and Electron Spin
Chemical Bonding: Lectures 7-9
Molecular Orbital Theory
Energies and electron densities 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
Websites:
www.chem.iitb.ac.in/academics/menu.php
(CH103 Course Material for 2008 and 2009); ,
IITB-Moodle http://moodle.iitb.ac.in
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
reshaping the modern world?
All of Science and Engineering is moving towards
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
4. Atmospheric Science Have to Save the World
Organic Light Emitting Diodes (O-LEDs)
LEDs from Conducting Polymers: MEH-PPV
Plastic Electronics and Displays
Conducting-polymers are replacing liquid crystals
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
Molecular Electronics
Mechanics of Electrons and Atoms
Nano-science
And Nanotechnology
Mult-electron Atoms
(Periodic Table)
Electron
Microscopy
Intermolecular Forces
And Interactions
Multi-atomic
Bonding, Molecular
Structure
Biology,
Materials Science
Condensed Matter
Physics
Chemical Reactions
Molecular Dynamics
Atomic/Molecular
Spectroscopy
Atomic Structure - History
Plum-Pudding Model
J.J. Thompson (Discovered Electrons, 1996)
Rutherfords Gold Foil Experiment
Rutherford beamed alpha particles (++) through gold foil and detected
them as flashes of light on a screen. The gold foil was only
0.00004 cm thick, meaning on a few hundreds of atoms thick
1871-1937
Planetary model loggerheads with
classical electromagnetic theory
Classical EM theory can not explain
Blackbody Radiation
Theories based on classical physics unable to explain temperature
dependence of emitted radiation (radiant energy density)
Sun, starshot iron rod
All classical theories
led to the so called
Ultraviolet Catastrophe
2
3
8
( ) ;
b
k T c
T d d
c

= =
Max Planck assumed energies of
oscillators are discontinuous
3
/
( )
1
v
bv t
a
T d
e

Energy of electronic oscillators

were discrete, integral multiple of frequencies
E = Energy of electronic oscillators
v = frequency of electronic oscillators
h = Plancks constant = 6.626 x e
-34
joule-sec
Note: h came in as a fitting parameter
Osc
E nh =
1858-1947
Planck never believed his theory was right, since he was a classical physicist
3
3
/
8
( )
1
B
v
h k T
h d
T d
c
e



| |
|
\ .
=

Line Spectra of Atoms

Rydbergs formula:
1 2
2 2
1 2
1 1 1
;
H
R n n
c n n

| |
= = = >
|
\ .
R
H
= 109677.57 cm
-1
1854-1919
Bohrs Phenomenological Model
(orRutherford-Planck-Bohr Model)
Electrons rotate in circular orbits around
a central (massive) nucleus, and obeys
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
The Atom in a stationary state does
not emit electromagnetic radiation
When an atom makes a transition from
one stationary state of energy E
a
to
another of energy E
b
, it emits or absorbs
a photon of light: E
a
E
b
= hv
1885-1962
Bohrs model explains atomic spectra
n=1,2,3,...
2
(2 )
nh
mvr
r n

=
=
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

| |
= = =
|
|
\ .
Spectral Transitions: E=hv
Further details in Tutorials as problems!
Explains Rydbergs Formula
4
2 2 2
0
1
.
8
e
n
m e
E
h n
=
Photoelectric Effect
1. Increasing the intensity of the light
increased the number of photoelectrons,
but not their maximum kinetic energy!
2. Red light will not cause the ejection of
electrons, no matter what the intensity!
3. Weak violet light will eject only a
few electrons! But their maximum kinetic
energies are greater than those for very
intense light of longer (red) wavelengths
0
2
0
( )
Wave Energy related
to
of
E E Sin kx t
Intensity E
Independent

Photodetectors, Photovoltaics,
Elevator sensor, smoke
detectors
Experimental Observations
Einstein: light can behave like particles
2
0
Energy to remove e' from surface
1
2
0
P M
M
E hv KE mv
KE hv

=
= = + = +
=
Borrowing Plancks idea that E=hv, Einstein further proposed that radiation
itself existed as small packets of energy (Quanta), now known as PHOTONS
P
E h =
1879-1955
Nobel prize for
Photoelectric effect
Energy of photon
freq. dependent
Light is EM Radiation: Waves
Diffraction or Interference Pattern can be possible only if light is a wave
10
( )
( )
~ 3 10 / sec
m
m
m
m
E E Sin kx t
B B Sin kx t
E
c cm
B

=
=
=
Wave-Particle Duality of Light
Light has both
wave-like and
particle-like
properties
even though
not observed
simultaneously
De Broglie Hypothesis: Matter Waves
h h
p mv
= =
Since Nature likes symmetry, particles also should have wave-like nature
Wave-Packet
1892-1987
-34
10
-31 6
6.6x10 J s
7 10
9.1x10 Kg 1x10 m/s
h
m
mv

= = =

Electron-wave moving @ 10
6
m/s
too small for
MACROSCOPIC
OBJECTS
Electrons are well known particles
with a negative charge
J.J. Thompson, Nobel Prize in 1906
FOR SHOWING ELECTRONS ARE
PARTICLES
Essentially how a CRT
Monitor or standard TV
works
Electron show interference patterns
Waves
Davisson and Germer 1927
J.Js son, George Thompson, Nobel Prize 1937
For showing ELECTRONS are WAVES
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
Bohr Model with a De Broglie Touch
Constructive Interference
Of the electron-waves
Can result in stationary
States (Bohr orbits);
If wavelength dont match,
There can not be any
Energy Level (state)
2 n=1,2,3,...
n=1,2,3,...
2
r n
h
mv
nh
mvr

=
=
=
Uncertainty Principle - Heisenberg
.
4
x
h
x p

IMPORTANT FOR SUB-MICROSCOPIC SYSTEMS
h = 6.626 x 10
-34
J s
1901-1976
Further details in Tutorials as problems!
Uncertainty Principle: X.P
x
~
Wave-Packet
Specifying position accurately would require many
waves, each having a fixed value of momentum (k),
P becomes Completely uncertain.
If only one wave with known k (momentum),
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
evidence, and then proceed to describe it
in terms/quantities which we know from our
experience of the macroscopic world.
Classical quantities such as position and
momentum have decreased suitability for
describing the physics of the subatomic
world.
Need a new theory for dynamics of
electrons, atoms or molecules
Probabilistic, not deterministic (non-newtonian)
Wavelike equation for describing sub/atomic systems
Schrodinger 1925!!!
Mathematical Tools Required

1
0
4, , , , , , / ( ) ( ) :
d
SQR CUBE Sin new functions numbers
dx y
Af x g x

=

1. Operators: A symbol that tells you to do something to whatever follows it.
Operators can be real or complex, and can be represented as matrices. An operator
Essentially perturbs a function or system, as if a measurement is being done!
2. Solve 2
nd
order partial differential equations with multiple variables:
2 2
2 2
( ) ( ) ( ) ( )
( ) ( )
f f f f
m
x y x y
f x nf y k
x y x y
+ +

+ + + =

2
2
( )
( )
f x
kf x C
x

+ =

2 2
2 2
( ) ( ) ( ) ( )
( ) ( )
f f f f
m
d x d x d y d y
f x nf y k
dx dy dx dy
+ + = + + =

| |

1 1 2 2 1 1 2 2
3

( ) ( ) ( ) ( ) : ;
but or , : Operators
Quantum Mechanical Operators are Linear Operators
d
A c f x c f x c Af x c Af x Linear
dx
SQR or Sin Cos Nonlinear

+ = +
Separation of
Variables
2 2 2
1 1
: ( ) ( ) and ( ) ( )
n n
j j j j j j
j j
Mean E x x x P x E x x x P x
= =
= = = =

4. Expectation Values or Average or Mean values

, ( ), ( ) ( ) : Given A find the function x such that A x a x Eigenvalue Equation =
3. Eigenfunctions and Eigenvalues:
Operator operating on a function results in re-generating the same function
(which is called eigenfunction) multiplied by a number (eigenvalue)

; ? ? ( )
n
x
n
d
Can or Sin x Eigenvalues
dx
A x be e

=
If P(x) is the probability
(#) for , , but (#) for ,
n
n
d
Sin x Sin x n even it is Sin x n odd not eigenfucntion
dx
= = =
! :
n
x n x n
n
d
Yes EV
dx
e e

=
LAWS of Quantum Mechanics
The state of a system is completely specified by the
wavefunction (x,y,z,t). Its square gives probability density
To every observable in classical mechanics, there corresponds a
linear operator in quantum mechanics
In measurement of observable associated with operator A, only values
that will be observed are the eigenvalues of A
The average value of the observable corresponding to A is
(x,y,z,t) of a system evolves according to time-dependent Schrodinger Eqn:

* a A d =

1. Born Interpretation of Wavefunction

1. The state of a QM system is completely specified by a wave
function (x,y,z,t) & all possible information can be derived from
Y can be real or complex
2. *. dv is the probability that the particle lies in volume
element dv, so

is the probability density at that point

1882-1970
y
x
z
x
a
y
a
z
a
dx
dy
dz
*
2
1 3 : ( , , , ')
Pr( , , )
( , , , '). ( , , , ')
( , , , ')
a a a a a a
a a a a a a
a a a
Particle System in D x y z t
x x x dx y y y dy z z z dz
x y z t x y z t dxdydz
x y z t dv

+ + +
=
=
*
2
* 2 2
:
( )( )
can be complex f ig and f ig
f ig f ig f g
= + =
= + = + =
1a. Corollary: Normalization
* *

( , , ). ( , , ) 1
all space all space
x y z x y z dxdydz d = = =

Normalization of Wave function: Since dv is the probability, the total
probability of finding the particle somewhere in space has to be unity.
If integration diverges, i.e infinity: can not be normalized, and therefore can
NEVER be an acceptable wave function. But if it is a constant A 1, then it is OK
Work on problems related to normalization of wave functions
Automatically, a condition has been imposed on the nature of wave function :
must vanish at infinity, or rather at the boundaries! Also has to be finite!!!
X

The state of a QM system is completely specified by a wavefunction

which is (x,y,z,t). Square gives probability density
To every observable in classical mechanics, there corresponds
a linear operator in quantum mechanics
In measurement of observable associated with operator A, only values
that will be observed are the eigenvalues of A
The average value of the observable corresponding to A is
(x,y,z,t) of a system evolves according to time-dependent Schrodinger Eqn:

* a A d =

LAWS of Quantum Mechanics

2. Classical Correlation
To every observable in classical mechanics, there corresponds
a linear operator (real or complex) in quantum mechanics

Classical quantity Quantum Mechanical operator

Position, x
x


Momentum, p
x
dx
d
ih


Kinetic energy in 1-D,
2
2
x
x
p
K
m
=
2
2 2
2 dx
d
m
h

Kinetic energy in 3-D,
( )
2 2 2
1
2
x y z
K p p p
m
= + +

|
|
.
|

\
|

2
2
2
2
2
2 2
2 z y x m
h



Potential Energy, V(x) Multiply by V(x)

Total Energy, E= K+V |
|
.
|

\
|

2
2
2
2
2
2 2
2 z y x m
h
+ V(x)
Find out QM operators corresponding to angular momentum, and KE for rotating systems
The state of a QM system is completely specified by a wavefunction
which is (x,y,z,t). Square gives probability density
To every observable in classical mechanics, there corresponds a
linear operator in quantum mechanics
In measurement of observable associated with operator A,
the only values that will be experimentally measured are
the eigenvalues of A, (which can not be imaginary)
The average value of the observable corresponding to A is
(x,y,z,t) of a system evolves according to time-dependent Schrodinger Eqn:

* a A d =

LAWS of Quantum Mechanics

3. Real (observable) eigenvalues
(even if is often Imaginary)

n n n
A a =
In any measurement of bservable associated with operator A, the only values that
will be ever observed are the eigenvalues a
n
, which satisfy the eigenvalue equation:
Only real eigenvalues will be observed, which will specify a number
corresponding to the classical variable for the particular eigenfunction
All the eigenfunctions of Quantum Mechanical operators are Orthogonal
*
( ) ( ) 0 for
m n m n
x x dx m n
+

= =

n
corresponds to the eigenfunctions or
eigenstates of the system.
Eigenvalues represented by a
n
are observables
If the system is in state
k
, a measurement on
the system will yield an eigenvalue a
k
There may be, and typically are, many
Eigen-f(n)s for the same QM operator!
The state of a QM system is completely specified by a wavefunction
which is (x,y,z,t). Square gives probability density
To every observable in classical mechanics, there corresponds a
linear operator in quantum mechanics
In measurement of observable associated with operator A, only values
that will be observed are the eigenvalues of A
The average value of the observable corresponding to A is
(x,y,z,t) of a system evolves according to time-dependent Schrodinger Eqn:

* a A d =

LAWS of Quantum Mechanics

4. Average or Expectation value
2
*
( ) ~ . ( 1 ) P x dx dx in D =
Prescription for obtaining the average or mean value of a classical observable
<a> corresponds to the average value of a classical physical quantity or
observable, and A represents the corresponding Quantum mechanical operator


*
all space
a A dv A = =

nd 2 2
( ) ( ) and 2 moment ( ) E x x xP x dx x x P x dx
+ +

= = =


2
*

1 . ( ) = . ~
all space
In D a A P x dx A dx A dx
+ +

=

The state of a QM system is completely specified by a wavefunction
which is (x,y,z,t). Square gives probability density
To every observable in classical mechanics, there corresponds a
linear operator in quantum mechanics
In measurement of observable associated with operator A, only values
that will be observed are the eigenvalues of A
The average value of the observable corresponding to A is
(x,y,z,t) of a system evolves according to time-dependent
Schrodinger Equation:

* a A d =

( , ) ( , ) i r t H r t
t

h
LAWS of Quantum Mechanics
5: Schrodinger Equation (SE)
1887-1961
The SE equation is somewhat equivalent to Newtons laws,
but applicable to atomic (molecular) and subatomic systems

2
2 2
2
(1 )
2 2
x
x
P D i
x
P
K
m m x

= =

h
h
Predicts the probability of finding the particle at a
Specified volume element at future time
counterpart to Newtons Equations of classical motion.

2
2
For ( , ),
( , ) ( , ) ( , )
2
x
x t Schrodinger Equation
i x t V x t x t
t m

= +

h
h

2
2
2
2
2
( )
( , )
2
, 1
x
x
Hamiltonian Energy Operator
H V x t
m
where in D
x
= +

h
2
nd
order partial differential equation
Time evolution of the wavefunction is somehow
related to the total energy of the system/particle

Classical quantity Quantum Mechanical operator

Position, x
x


Momentum, p
x
dx
d
ih


Kinetic energy in 1-D,
2
2
x
x
p
K
m
=
2
2 2
2 dx
d
m
h

Kinetic energy in 3-D,
( )
2 2 2
1
2
x y z
K p p p
m
= + +

|
|
.
|

\
|

2
2
2
2
2
2 2
2 z y x m
h



Potential Energy, V(x) Multiply by V(x)

Total Energy, E= K+V |
|
.
|

\
|

2
2
2
2
2
2 2
2 z y x m
h
+ V(x)
Time-Dependent Schrdinger Equation
1 2 1 2
( , ,... , ) ( ). ( , ,... )
n n
x x x t f t x x x =
Very often, V(x,t) = V(x): solutions to the TDSE has the form:
i.e. The space part and the time part can be separated out in the solutions!
Maths: Separation of variables to solve linear 2
nd
order differential equations
2
2
1 2
( , ) ( , ) ( , ) ( , )
2
( , ) ( , ,... , )
x
n
i x t x t V x t x t
t m
x t x x x t

= +

=
h
h

2 2
2 2
2
( )
( , ) , 1
2
x x
Hamiltonian Energy Operator
H V x t where in D
m x

= + =

h
Separation of space and time variables
:
1 ( ) ( )

( ) ( )
dt
TIME DEPENDENT PART of solution
df t df t iE
E
i f t dt f t

| |
= =
|
\ .
h
h
| | | |
2 2
2
1 1 ( )
( ) ( )
2 ( ) ( )
LHS F(x) = RHS F(t) :
f t
V x E const
m x x i f t t
E independent of x and t

+ = =

h h

2 2
2 2
Let us consider the solutions for TDSE that have the form:
( ) ( )
( ) ( )
( , ) ( ). ( )
f t x
x and f t
t t x x
x t f t x

= =

=
For a one-particle, 1-D system, If V(x,t)=V(x):
2 2
2
: ( )
2
TDSE V x
m x i t

+ =

h h
Substitute & divide by ( ) ( ) f t x =
/
( ) ~
iEt
f t e
h
Time Independent Schrdinger Equation
2 2 2 2
2 2
Re ( ) :
1 ( )
( ) ( ) ( ) ( )
2 ( ) 2
arranging TIME INDEPENDENT SPACE PART
d x d
V x E V x x E x
m x dx m dx

+ = + =


h h
2 2
2
1 ( )
( ) dimension ,
2 ( )
. ( !!!)
d x
V x E E has same as V QM POSTULATES
m x dx
that the const E is the ENERGY of the system energy comes automatically

+ =
h

2 2 2 2
2 2 2
1
1 (3 ) :
( , , )
2
N
i
i i i i
For particle D system solve TISE
V x y z E
m x y z

=
| |

+ + + =
|

\ .

2 2
2
: ( )
( )
2
( ) ( )
Time Independent Schrodinger Equation Stationaty States
d
where H V x T V
m dx
H x E x

+ = + =
h
~ We have suddenly come up with another EIGENVALUE PROBLEM to solve!!!
N
H
n
=E
n

n
: Energies and Wavefunctions
( ) ( )
( )( )
2 2 *
/ * /
2
0 *

.
( )
iEt iEt
f f f
e e
e
F t

= =
=
= =

h h
For Stationary states (i.e. for a particular solution):
2
and Energy are
constant over time

2 2
2
, ( )
2
( ) ( )
n n n
where H V x Total Energy
m x
H x E x

+

=
h
MANY solutions to the TISE possible different with different energies
All energies are allowed unless there are some special conditions (just like a wave)
Does not mean that the
system is at rest (recap
Bohrs stationary state), but
energies and the probability
do not change with time.
Well-Behaved or valid wavefunctions
1. must be normalizable: must be finite and 0 at boundaries/ infinity
2. must be a solution of the Schrodinger equation:
A. Must be a continuous function of x,y,z.
B. The slope of the function i.e. d/dq must be continuous in x,y,z.
3. must be single-valued
Quadratically integrable
The essence of Quantum Mechanics
Not deterministic: Can not precisely determine many parameters
in the system, but can provide all the information (spatio-
temporal) of a system.
Only average values and probabilities can be obtained for classical
variables, now in new form of operators.
Total energy is conserved, but quantization/discretization of
energy levels come spontaneously from restriction on wave
function or boundary condition
Final outputs tally very well with experimental
results thats why QM is still out there! Does not
violate Classical mechanics for large value of mass.
Applications- 1. Free Particle

2 2
2
:
( )
( ) ( ) ( )
2
( ) ( )
Time Independent Schrodinger Equation
x
V x x E x
m x
H x E x

+ =

=
h
2 2 2 2
2
2 : : ( ) sin cos
( ) cos sin
2
( ) ( sin cos ) ( )
nd
Solve the Order Linear DE Trial Solution x A kx B kx
D x A kx B kx
mE
D x k A kx B kx k x k

= +
=
= + = =
h

2 2 2
2 2
2 2
2 2 2
:
( ) 0 : " "
( ) 2
( ) ( ) ( ) 0
2
For a free particle
V x as there are no external potential forces free
x mE
E x D x k x where D and k
m x x

=

= + = = =

h
h
2 2
;
2
2 2
( ) sin cos
k
E No restrictions on k Energies of free particle continuous
m
mE mE
And x A x B x
=
= +
h
h h
No Quantization:
All energies allowed
2. Particle in 1-D Potential Well
2 2
2
2
: ( ) ( ) ( ) 0 ( ) ( )
: ( ) 0
m
For regions I and III D x E V x D x x
Normalization condition not satisfied Only solution x

+ = =
=
h
2 2 2 2
2 2
2 2
: ( ) ( ) 0 ( ) ( ) 0
,
: ( ) sin cos
mE mE
For regions II D x x D x k x k
Similar to Free Particle solution but nowboundary conditions present
Trial Solution x A kx B kx

+ = + = =

= +
h h
Boundary Condition
(0)=0 and (L)=0
As continuous
V=0
V=
V=
Region I
Region II
Region III
X X=0 X=L
: 0, ( ) 0 0 ( ) sin
, ( ) 0 sin 0 0 sin 0
0, ( ) 0 !! sin 0 1, 2, 3, 4,...
Boundary Conditions x x B x A kx
Also at x L x A kL either A or kL
If A x everywhere or kL kL n n

= = = =
= = = = =
= = = = =
Particle in Box (PIB) Energies are
Quantized: Certain Levels Allowed
2
2 2 2 2 2
2
2 2 2
2
:
sin 0 for 1, 2, 3, 4,...
2
2 8
, n=1,2,3,4,...
,

n
n
From Boundary Conditions
kL kL n n
m n n n h
E k E
L mL mL
or E n
Automatically energy is no longer continuous
but discrete or quantize

= = =
| |
= = = =
|
\ .
=
h
h
!!! d
Note: minf. energies merge
Llarge, energies merge
2
2 2
2
1 :
( )
8
Larger ,
i f
f i f i
Spectroscopy of PIB in D n n
h
h E E E n n
mL
the box smaller the energy of hv

= = =
Zero Point Energy
Concept!
PIB Wave Functions and Probabilites
* 2 2
0 0
: ( ) sin sin
: ( ) ( ) 1 sin 1
2 2
: ( ) sin
L L
n
n
Wavefunction x A kx A x
L
n
Normalization x x dx A x dx
L
n x
Solve for A Normalized Wavefunctions x
L L L

= =
| |
= =
|
\ .
= =

# of Nodes
(zero
crossings)
= n-1
Symmetric
(even function)
And Anti-
Symmetric
(odd function)
Expectation Values and Probability
Particle in a 2-D Well: Approach
Particle in a 2-D Well: Energies
2D Well: 2 Quantum Numbers are required to describe the system
V=0
2
2 2
,
2 2
, , 1, 2, 3, 4,....
8
x y
y
x
n n x y
x y
n
n h
E n n
m L L
| |
= + =
|
|
\ .
Degeneracy is manifestation of symmetry
2-D Potential Well - Wavefunctions
What Quantum Numbers in x and y
do this wavefunction correspond to?
Number of nodes = n
i
-1
Particle in a 3D-Box:Wavefunctions
3-D Box: 3 Quantum Numbers
Cubic Box: Wavefunctions
Importance in Chemistry/Spectroscopy
Electronic spectra of conjugated molecules (loose p-electrons): 1D-PIB
V=0
V=
V=
Region I
Region II
Region III
X X=0 X=L
2
2 2
2
1 :
( )
8
,
i f
f i f i
Spectroscopy of PIB in D n n
h
h E E E n n
mL
Longer the box smaller the energy of hv

= = =
Increasing length of the box
(i.e. the conjugation length)
reduces the energy gaps and
hence lower energy photons
are absorbed or emitted
Nanoscience: Quantum Confinement
Band gap changes due to confinement,
and so will the color of emitted light
CB
VB
CB
VB
CB
VB
Quantum Dots Particle (excitons) in a Sphere!
Quantum Dots have a huge application
In chemistry, biology, and materials science
For photoemission imaging purpose,
As well as light harvesting/energy science
- + - + - +
The Hydrogen Atom
A Completely Solvable 2-body problem!!
(kind of rare, in Quantum Mechanics!)
What we learnt from solving PIB?
Formulate a correct Hamiltonian
(energy) Operator H
Impose boundary conditions
for eigenfunctions (restriction)
and obtain Quantum Numbers
Probabilites and
Expectation Values
Solve H=E (2
nd
order PDE)
by separation of variable and
intelligent trial/guess solutions
Energies etc. of states
Corresponding to
Quantum Numbers
Eigenstates or Wavefunctions:
Should be well behaved -
Normalization of Wavefunction
Quantum Numbers
that specify the
state of the system
H-Atom: Constructing H=T+V

2
2 2 2 2
2 2 2
1
( , , )
( , , , ) ( , , , )
2 2
( , , , )
N
i
i i i i
P x y z
H KE PE V x y z t V x y z t
m m x y z
P i and V x y z t Potential energy
x y z
=
| |

= + = + = + + +
|

\ .
| |
= + + =
|

\ .

h
h

2 2
2 2

2 2
Nucleus Electron
Electron Nucleus
Nucleus Electron
m m
H V

+ =
h h
Hydrogenic Atoms: 2-Particle System
1 electron moving around a
(massive) central nucleus (+ve)

2 2 2
2 2 2
2
2 2
1
, ( ) ;
2
i i i
N
i i
i i
where Laplacian i particles
x y z
H V
m
=

= + +

= +

h
r

2 2
2 2

2 2
Electron Nucleus
Nucleus Electron
Nucleus Electron
m m
H V

+ =
h h

( ) ( ) ( )
2 2 2 2 2 2 2 2
2 2 2 2 2 2
2 2 2
2
2 2

N N N N e e e e
e N e N e N
m x y z m x y z
where r x x y y z z
Ze
r
H
| | | |

+ + + +
| |

\ . \ .
= + +
=
h h
2 2 2
2 2
,
,
2 2
( , , , , )
e e e N N N Total e N
N e
Total
e
N Total Total Total Total Total
Ze
m m r
where x y z x y z and E E E
E
=
=
= +

h h

2 2
0
: ( ) ( ) ~
4
Coulomb Potential
Ze Ze
Potential Energy V U r
r r
= =
r
Potential Energy: Coulomb Potential
:
Total
If Complete Wavefunction for H Atom TISE becomes =
Reduced Form of TISE for H-Atom:
Separation of Variables



Reduced Center of Mass:
e e N N
e N CM
e e N N
e N CM
e e N N
e N CM
e N
m x m x
x x x x
M
m y m y
y y y y
M
m z m z
z z z z
M
m m
M
u
+
= =
+
= =
+
= =
=
2
2 2
2
2

2
2
in terms of CM and electronic coordinates
( , ) ( ) ( )


, , , , , , , ,

N N N
Total e e e N N N e e e e N N N N
CM
e e e e
E
M
Ze
r
Separate H
and
E
x y z x y z x y z x y z
u
=
=
=
| |
|
\ .

h
h
Free Particle: movement of
The whole atom: You solved it!
Relative motion of the electron and
With respect to the Nucleus
2 2 2 2 2
2 2 2
2 2 2
( , , ) ( , , ) ( , , ) ( , , ) ( , , )
2
e e e e
i i i
e e
Ze
x y z x y z x y z x y z x y z
x y z
x y z
E
u
=
| |
+ +
|

+ + \ .

h
Problem: 2
nd
order PDE with 3 variables - can not be separated!
Relative motion of electron wrt nucleus:
:
.
Movement of electronmuch faster than heavy nucleus
Separate translational motion relative frame
Spherical Polar Coordinates
Hamiltonian (Energy) Operator in
3D Spherical Polar Coordinates
To solve this PDE, need to separate variables, which is POSSIBLE
TISE for H-Atom in spherical-polar
coordinates

s ( ) ( ) ( ) : ( , , ) ( ) ( ) ( ) Special olution if H H r H H r R r = + + =
| | | |
| |
2
2
2
2 2
2
2
1
( ) ( ). ( ) sin ( ) ( ). ( )
sin
1
1
( ) ( ). ( )
sin
2

d d d d
r R r R r
dr dr d d
r
d
R r
d
Ze
E R
r




u

| | | |
+
| |
\ . \ .


+


| |
+ +
|
\ .
h
( ) ( ) ( ) 0 r =
2
2
2 2 2
2
2
1 1 1
( , , ) sin ( , , ) ( , , )
sin sin
2
( , , ) 0
r r r r
r r r
Ze
E r
r


u


| | | |
+ +
| |

\ . \ .

| |
+ +
|
\ .
=
h
2
nd
order Partial Differential Equation with three variables
2 2 2
2 2 2
2 2
sin sin 2 1
sin sin
d dR d d Ze d
r E r
R dr dr d d r d
u


| |
| | | |
+ + + =
| | |

\ . \ .
\ .
h
2
( , ) ( ) ( , ) ( ) . ( ) LHS F r F RHS F r F Const m say = = = = = =
2 2
2
2 2 2 2
1 2
sin 0
sin sin
d dR R d d R d Ze
r E R
r dr dr d d d r
u

| |
| | | |
+ + + + =
| | |
\ . \ .
\ .
h
2
2
2
1
0 m

+ =

2 2
sin
:
. .
r
Multiply by and rearrange
R

Separation of Variables r, ,
( , , ) ( ). ( ). ( ) . . r R r R = =
Solve 2
nd
order DE to obtain
functional form of ()
: ( ) Solution
im
Ae

=
Solving -part is relatively simple!
Another Quantum Number popped out out of Boundary Conditions:
Quantization of Angular Momentum!
Magnetic Quatnum Number: Theoretically can take any integral value including
Zero, but restricted by another quantum number, l: m<l. Related to orbital
Angular momentum and splitting of energy levels in presence of magnetic field.
Boundary Condition
2
2
2
1
( ) 0
( )
m

+ =

2
2
2

&
im
m

Solving R(r) and () part not so simple,

but can be done!
2 2 2
2 2
2
2
sin sin 2
sin sin 0
d dR d r Ze
r E
R dr dr d r
m
u


| |
| | | |
+ + + =
| | |

\ . \ .
\ .

h
Need mathematical skills to solve the Differential Equations for R(r) and ()
2 2 2
2
2 2
1 2 1
sin ( ) .
sin sin
d dR r Ze d d m
r E say const
R dr dr r d d
u


| |
| | | |
+ + = + = =
| | |

\ . \ .
\ .
h
Only r : Can be solved
to obtain R(r) part
Only : Can be solved
to obtain () part
2
sin : Divide by and rearrange
()() are Spherical Harmonics Y
l
m
(.)
l=Azimuthal Quantum Number
or orbital quantum number ln-1
Easier to solve if written differently: Rigid-Rotor Problem already
have solved the angular (q, f) part: Related to Angular Momentum!
L
2
Square of angular momentum: Eigenfunctions are Spherical Harmonics
n= Principal Quantum Number=1,2,3,
Radial Wavefunction depends on n and l:
Solve for R(r): Quantized Energies
Only n dependence of E: Note that V term in the H is needed for
providing energies as eigenvalues. Angular parts did not have it!!!
Essentially same
Equation as Bohrs,
With slight changes
Energies: E
n
:
Meaning of Quantum Numbers
L=0 s-orbital
L=1 p-orbital
L=2 d-orbital
L=3 f-orbital
Normalization
Radial Solutions depend on n and l (l=n-1)
Additional restrictions on l: n l +1
2 1
0
0
2
( , ). . .
l l
nl n l
Zr
na
Zr
na
R A n l r L e
| |
|
+
\ .
+

| |
=
|
\ .
f(r,n,l,Z) g(r,Z)
Exponential
Decay g(r)
Note: R
nl
0 as rinfinity
H-Atom Complete (r,.) for n=1,2
r/a
0
F(r) only
Linear combination
Of two solutions is
Also a solution
(linear operators!)
1S
2S
2p
z
2p
x,y
F(r,)
F(r,.)
F(r) only
S-Orbitals (l=0,m
l
=0) R
nl
and R
nl
2
Seems that the maximum probability of finding the electron on the nucleus itself
100 ' / 2
1S
N e

=
200 '' / 2
2
(2 )
S
N e

=
300 ''' 2 / 3
3
(27 18 2 )
S
N e



= +
Surface plot of and
2
for S
1S
2S
(1S)
2
(2S)
2
Surface plot of and
2
for 2p
Surface plot of and
2
for 3d
R
2
(r) predicts maximum probability
at the center of the atom (for s)!!!
2 2
2
2 2 2
Probability

4 ( ) ( )
increasing
4 ( ) 0 4 0
nl
nl
of finding the electron
anywhere in a shell of thickness
dr at radius r is r R r dr for S
r funtion
r R r dr as r dr

Product
of increasing
function and
decreasing
function:
MAXIMUM
Radial Distribution Functions: 4pr
2
R
nl
2
(r)
Number of Radial Nodes
is always n-l-1
3s: n=3, l=0
Nodes= 2
3p: n=3, l=1,
Nodes= 1
3d: n=3, l=2
Nodes = 0
N=1, l=0
N=2, l=0
N=3, l=0
nS nS
r r =
Shapes of orbitals depend
on Orbital quantum number l
and Magnetic quantum no. m
l
No dependence: symmetric around z axis
Angular Distribution Functions
Color or Shading
Related to Sign
of wavefunction
/ 2
/ 2
(2 ) .sin .cos
(2 ) .sin .sin
x
y
p N e
p N e

=
=
/ 2
210
(2 ) .cos
z
p N e

=
2
2 2
2 2 / 3
1
2 / 3
2
2 / 3
3
2 2 / 3
4
2 2 / 3
5
3 (3cos 1)
3 sin cos cos
3 sin cos sin
3 sin cos 2
3 sin sin 2
z
xz
yz
x y
xy
d N e
d N e
d N e
d N e
d N e

=
=
=
=
=
d-orbitals: n=3, l=2, m
l
=-2,-1,0,1,2
Angular Part
Angular + Radial
Blue: -ve
Yellow: +ve
f-orbitals: n=4,l=3,m
l
=-3,-2,-1,0,1,2,3
Cross Sections of Orbitals:
Highly Symmetric Visual Treats
Radial parts not to scale!
How do they look from outside in 3D?
Radial parts not to scale!
How do they look from inside in 3D?
Radial parts not to scale!
Can you guess what orbital this is?
What are the quantum numbers?
Why did we talk about all these
complex orbitals when there is
only one electron in H-atom?
Excited Electronic States!
Basis for all kinds of spectroscopy!
Multi electron systems: Orbitals
are not that different!
Multi-Electronic Atoms
More than 1e: Can not be solved exactly!
He-atom (2e): 3-particle system!
+
1
2
r
1
r
2
r
12
=r
1
-r
2
In atomic units, for convenience, often constants m
e
,e, 4
0
, h/2 are omitted

1 2
1 2 1 2 1 2 1 2
12
1
( , ) ( , ) ( , ) ( , )
He
H r r H r r H r r r r
r
= + +

1 2
12
1
electronic
He H H H
r
= + +
Multi-electron atoms
Hamiltonian is no longer
spherically symmetric
due to (1/r
12
) term and
therefore numerical
methods must be used
to solve the TISE
H
i
1 electron hydrogenic Hamiltonians for each particle
Such that H
i

i
=E
i

i
, where E
i
are 1-electron energies

1 1 1 2 2 2
1 2
1
( , , , , , ,...... , , ) ( , , ) .
N N
N N N i i i i
i i j
ij
H r r r H r const
r

= < =
= +

Inter-electronic interaction
terms mess things up!
Orbital Approximation for N electrons
1 electron wavefunctions are termed orbitals!
Implies that e-e interaction is
neglected, as first approximation!!
TISE for He: 2 electron system

1 1 1 2 2 2 1 1 1 2 2 2
1 1
1 2
1 1 1 2 2 2
12
( , , , , , ) ( , , , , , )
1
( , , ) ( , , )
He
He He He
e e
He
H r r E r r
H H r H r
r


=
= + +
1 1 1 2 2 2 1 1 1 1 2 2 2 2
( , , , , , ) ( , , ) ( , , ) ( 1 )
He
r r r r product of e wavefunctions
Orbital Approximation (for He)
3 3
2 2
0 0
1 2
0 0
1 1
1 (1)1 (2) .
He
Zr Zr
a a Z Z
s s
a a
e e


| | | |

| |
\ . \ .

1 1
1 1 1 1 1 2 2 2 2 1 1 1 1 2 2 2 2 2
( , , ) ( , , ) ( , , ) ( , , )
e e
He H r r r r = +

Hydrogenic orbitals since both electrons will be in the 1s orbital!

1 1
1 2
1 1 1 1 2 2 2 2 1 1 1 1 2 2 2 2 1 1 2 2
12
1 ( ) :
1
( , , ) ( , , ) ( , , ) ( , , ) ( ) ( )
e e
He
In order to solve for e orbital energies NEGLECT Electron Electron REPULSION
H H r r r H r r r
r

= + +

| | | |
1 1
1 1 1 1 1 2 2 2 2 2 1 1 1 1 2 2 2 2
( , , ) ( , , ) ( , , ) ( , , )
e e
He H r r r r = +

( )| |
1 1 1 1
1 2 1 1 1 1 2 2 2 2 1 2
( , , ) ( , , )
e e e e
He
He He
H r r E E = + = = +
2 4 2
1 2 1 2
2 2 2
1 1
1 2
( ) 13.6 4( 13.6) 108.8
. : 24.6 54.4
IE IE
Z e Z
E Theory eV eV E E E E eV
n n
Exp Ionization Energies E eV E eV
u
= = = = = + =
= =
h
Most serious assumption of orbital approximation is incorrect !
Electrons stay out of each others way by undergoing correlated
Motion to ensure electronic repulsion is minimum
Need to use other (numerical) approximate methods such as Variational Method
or Perturbation Theory without using orbital approximation
Orbital Approximation is too Drastic
Let us find out what the ionization energies come out to be:
For He: Z=2,
n=1 (GS), say a=a
0
Electrons must be shielding each other!!!
Outer electrons feel that the net charge on the nucleus
is less than what is expected: Screening of Z
Effective Nuclear Charge
1 1 2 2
12
1
( ) ( ) , ! r r not small cannot be neglected
r

+2
Electronic Shielding: Effective Nuclear Charge
Effective nuclear charge is same for electrons in the
same orbital, but greatly varies for electrons of different
orbitals (s,p,d,f) and n. Z
eff
determines several chemical
properties of multi-electron systems
+2
3 3
2 2
0 0
1 2
0 0
1 (1)1 (2) .
eff eff
He
eff eff
Z r Z r
a a
Z Z
s s
a a
e e

| | | |

| |
\ . \ .
Multi-electronics: Consequences of Z
eff
How do we get 2p energy higher than 2S?
How does Radial distributions change?
How does Z
eff
affect atomic properties?
Read up on
electronic
configuration of
multi-
electronic atoms:
Hunds Rule
& Aufbau Principle
Quantization of Spatial (Orbital) Angular
Momentum of Electrons in the atom
L=2m
l
+1
Na/Ag atoms: ns1: l=0:
Zero Orbital Momentum
For 1S electrons
If electrons are classical, "spinning" particles, then distribution of their spin angular
momentum vectors is taken to be truly random and each particle would be deflected
up or down by a different amount, producing an even distribution on screen.
But electrons are deflected either up or down by a specific amount.
2s+1=2 => s=1/2
Intrinsic angular momentum or Spin
of an electron is quantized
This can only mean that spin angular momentum is quantized (i.e., it can only take on
discrete values). There is not a continuous distribution of possible angular momenta.
Electrons are spin-12 particles. These have only two possible spin angular
momentum values, called spin-up (or ) and spin-down (or )
The exact value in the z direction is m
s
= +/2 or /2. If this value arises as a
result of the rotating particles, then they would have to be spinning impossibly
fast (GREATER THAN THE SPEED OF LIGHT).
Spin S() where w is an unknown (internal, if exists) coordinate (NON-CLASSICAL)
Implication of Spin on Hydrogen 1-e
wavefunctions: Spin Orbitals
Introduction of spin results in the 4th quantum number
For each electron: 3 spatial, and one for spin (4
th
coordinate)
Introduce a spin component to each of the 1e WFs along with spatial
components. This doubles the degeneracy of each level little effect on energy.
1e WFs are now called SPIN ORBITALS.
2e Spin orbitals and Exclusion Principle
The complete wavefunction (both spatial and spin coordinates) of system of
identical fermions (i.e. electrons) must be anti-symmetric with respect to
interchange of all the coordinates (spatial and spin) of any two particles.
(Paulis?) Exclusion Principle: (by Dirac and Heisenberg)
Wavefunctions must reflect the indistinguishibility of electrons: The last
two functions are not allowed since they distinguishes between electrons
(1, 2) (2,1)
( )
Indistinguishibility
Exchange Operator
=
Symmetric:
Anti-symmetric:
Postulate 6: Complete wavefunctions describing a many electron system
must be antisymmetric under the exchange of any two electrons.
For He atom ground state (both electron is 1s):
Space part is SYMMETRIC: 1s(1).1s(2) since both e in same orbital
We must therefore multiply this with an ANTI-SYMMETRIC Spin function
Spin Part:
(1,2)(2,1)
6
th
LAW of Quantum Mechanics
Total Approximate of He (GS): 1s(1)1s(2) * 2
-1/2
[(1)(2)- (1)(2)]
Which is also anti-symmetric wrt exchange of electronic coordinates
Also, two electroncs is 1s orbitals have OPPOSITTE Spins!!!
Ground and excited states of He
Ground state: Both electrons are in same orbital (1s): 1s(1)1s(2)Symmetric
If they are in different orbitals: spatial part: 1s(1)2s(2) or 1s(2)2s(1)
Both these are neither symmetric nor anti-symmetric.
Spatial Part can only be: 1s(1)2s(2) + 1s(2)2s(1) (SYMMETRIC)
or 1s(1)2s(2) - 1s(2)2s(1) (ANTI-SYMMETRIC)
Complete (spatial & spin) wavefunctions for an excited state of He
(Note: Spatial*Spin part is antisymmetric)
Molecular Electronic Structure
and Bonding in Diatomic and
Polyatomic Molecules
Simplest Molecules: H
2
+
and H
2
For H
2
Molecule (2 Nuclei + 2 Electrons):
R
r
1A
r
1B
r
2A
r
2B
r
12

( ) ( )
2 2 2 2
1 2
1 2 1 2 12
2
H
1 1 1 1 1 1
~
A B e e
A A B B AB
H
r r r r R r
| |
|
\ .
| | | |
+ + + +
| |
\ . \ .

( ) ( )
2 2 2
1
1 1
2
H
1 1 1
~
A B e
A B AB
H
r r R
| |
|
\ .
+
| | | |
+ + +
| |
\ . \ .
H
+
2
Molecule Ion (2 Nuclei + 1 Electrons)
Born-Oppenheimer Approximation

+
2
2
H (1 )
1 1
1 1 1 1 1
~
H e
e A AB e B AB eB
H H
r R r R r
| |
+ = +
|
\ .
Nuclei are stationary
wrt electronic motion

( ) ( )
2 2 2
1
1 1
2
H
1 1 1
~
A B e
A B AB
H
r r R
| |
|
\ .
+
| | | |
+ + +
| |
\ . \ .
CONSTANT
Model 1: Valence Bond Theory (VBT)
1 electron in H1
2 electron in H2
Inclusion of ionic terms
Resonance
Model 2: Molecular Orbital Theory
Both VBT and MOT are used frequently each of
them work good for certain systems, respectively,
and often are not so good for other systems!
Molecular Orbital Theory: LCAO
Linear Combination of Atomic Orbitals (LCAO)
1 1 2 1 1 1 2 2
2 2 2 2 2
1 1 2 2 1 2 1 2
2
A B
MO Approx S S
MO
c c c c
c c c c


= = + = +
= + +
2 2 2
1 2 1 2 1 2
2 2 2
1 2 1 2 1 2
, ( ) ( ) ~1 1
, ( ) ( ) ~1 1
b b b b b A B
a a a a a A B
for c c c c c s s
for c c c c c s s


= = = + = + +
= = = =
2 2
1 2 1 2
, symmetry requires c c c c = =

+
2
Importance of Overlap Integral
2 2
1 2 1 2 1 1 2 2 1 2 2 1
? !
1 ( ) ( )
b a
b b b b
How to find out c and c Normalization
c c

= = + + = + + +

( ) ( )
1 2 1 2
1 1
;
2 2 2 2
b a
S S
= + =
+
S can be positive, zero or negative
S is a qualitative measure of bond strength
1 2 2 1
1 1
where
2 2 2 2
b a
c and c S Overlap Integral
S S
= = = =
+
1
1

( )

( )
1 1 1 1
/
1 1
2 2 2 2
A B A B
b b S S S S
b
E H H
S S

+
= = + +
+ +

1 1 1 1
/ /
Let
and
1 1
S S S S
i i j
i
ii ij
ii ij ii ij
b a
ij ij
H H and H H
H H H H
E E
S S

+
= =
+
= =
+
H
2
+
Bonding and Anti-bonding Orbitals
( )
( )
1 1
1 1
1
2 2
1
2 2
A B
A B
a S S
b S S
S
S


=

= +
+

1 1 1 1 1 1 1 1
/
1
=
2(1 )
A A B B A B B A
S S S S S S S S
b
E H H H H
S

+

+ + +

+

(1 )
1 1 1 1 1 1 1 1
.
1 1
( ) +
( )
B A B A B A B A
H e
ij BA S S S S S S S S
AB eB
const
H or H H H
R r


= =



(1 )
1 1 1 1 1 1 1 1
.
1 1
( ) +
( )
A A A A A A A A
H e
ii AA S S S S S S S S
AB eB
const
H or H H H
R r


= =



2
(1 )
1 1 1 1 1
~ H e
eA AB eB AB eB
H H
r R r R r
| |
+ = +
|
\ .
1 (1 ) 1 1
1 1
( ) where
A A
ii AA BB S e S S
AB eB
H or H H E J J Coulomb Integral
R r
= = + =
' arg arg Interaction energy of e viewed as a negative ch e clound on atom with a positively ch ed nucleus
1 1 (1 ) 1 1 1 1 1
1 1
B A B A B A
ij S S e S S S S S
AB eB
H E
R r
= +
Stabilization Energy due to Bond Formation
1 (1 ) 1 1
1
, where
Re :
.
B A
ij S e S S
AB eB
S
H E S K K
R r
K Exchange Integral or sonance Integral
Lowering of energy that leads to bond formation
= + =

K is purely a quantum-mechanical concept

1
S
H
2
+
: MO, Electron Density and Energy
H
2
+
Electron Density of Sigma Bonds
Bond formation With 1S-orbitals!
Note the signs, symmetries and nodes
LCAO-MO of p-orbitals
-bonding using p-orbitals
-bonding involving p-orbitals
Note the symmetries and the nodes
Symmetry and Nomenclature of MOs
Gerade (g) (symmetric) and Ungerade (u) (antisymmetric) wrt inversion!
Hydrogen molecule ion:
bBonding: symmetric
g
aantibonding: antisymmetric
u
*
Types of Covalent Bonds
What are the symmetries?
Where are the nodes?
What are the energies?
bonds
bonds
bonds
Dihydrogen Molecule (H
2
)
R
r
1A
r
1B
r
2A
r
2B
r
12
Place 2e with opp. spin in bonding orbital of H
2
+
| |
1
1
1 1
2(1 )
e
b A B
s s
S
= +
+
Can not be solved exactly Approximate
| |
2
1
1 (1)1 (2) 1 (1)1 (2) 1 (1)1 (2) 1 (1)1 (2)
2(1 )
MO
H A A B B A B B A
s s s s s s s s
S
= + + +
+
| || |
2
1
1 (1) 1 (1) 1 (2) 1 (2)
2(1 )
MO
H A B A B
s s s s
S
= + +
+
Spatial part!
| | | |
1
(1) (2) (1) (2) (2) (1)
2
bonding b b
=
| 1
i +
i +
[ ]
Space+Spin

2
2
2 2
H
1 2
1 2 1 2 12
H (1 ) (1 )
1 2 12
1 1 1 1 1 1
~
1 1 1 1
A B B A AB
H e H e
B A AB
H
r r r r R r
H H H
r r R r
| | | |
+ + +
| |
\ . \ .
= + + +
MOT overemphasizes ionic terms in a covalent bond! VBT better?
Dihydrogen Molecule: One more
electron goes to bonding orbital
Bond strength increases: Bond order=1
Effective nuclear charge changes the absolute energy
Levels and the size of orbitals!
Matching of energies of AO important for LCAO-MO
If energies are not close to each other, they would
Not interact to form MOs.
*
Energies of H
2
+
, H
2
, He
2
+
, He
2
He
2
+
He
2
Matching of AO energies for MO
Due to large difference in energy of 1s(H) and 1s(F), LCAO-MO for both
1S is not feasible in HF. Rather, 2Pz(F) and 1S(H) form a sigma bond.
Both symmetry and energy
Matching is required for MO.
Valence electrons are most important
H
2
Li
2
: core 1
Li
2
: core 1
Li
2
: Valence 2
Li
2
: Total
O
2
molecule
MO contours show electron densities
Total
2 and 2
3 and 1
1
MO contours: Total electron density
Maps of 1
st
row homonuclear diatomics
Expected MO and Energies for Dinitrogen
Is this these MO and correct energy level diagram for N
2
?
There is a problem! Spectroscopy says NO!
Actual MO and Energy Diagram for N
2
Mixing of 2S and 2P orbital occur because of small energy gap between them.
2s and 2p electrons feels not so different nuclear charge.
Note how the MO of 2ss have p-type looks, while pi-levels are clean
S-P Mixing: Hybridization of MO
Mixing of 2S and 2P orbital occur because of small energy gap between them.
2s and 2p electrons feels not so different nuclear charge.
S-P Mixing: B
2
confirms it!
Boron is paramagnetic. This can only happen if the two electrons with parallel
Spin are placed in the degenerate p-orbitals and if p orbitals are energetically
higher than the s* orbital
Incorrect!
MO and Energy Diagram for F
2
No Mixing of S and P orbital because of higher energy
Gap between 2S and 2P levels in Oxygen and Fluorine!
2s and 2p electrons feels very different nuclear charge
MO Energy Level Diagram
(Homonuclear Diatomics)
Bond order, strength, length
magnetic properties..from MO
Hetero-nuclear Diatomics: HF
Electronegativity of F
much more than H.
Electrostatic potentials
Can be computed which
Gives a realistic picture
Of the electron densities
In a bond: Egg Shaped
CO: Cases of S-P Mixing of two
atoms having different Z
eff
Hybrids: Linear Combination of S
and P leads to lowering of energy
Hybridization is close to VBT approach. Use of experimental information
All hybridized orbitals are equevalent and are ortho-normal to each other
Linus Pauling, ~1930
Linear Environment: s & 1-p mix: sp
Contribution from s=0.5; contribution from p=0.5
Have to normalize each hybridized orbital
S and P orbital of the
Same atom! This is not
The same as S (overlap)
2 equivalent hybrid orbitals
of the same energy and
shape (directions different)
Linear geometry with
Hybridized atom at the center
2S- and 2P- (similar energy)
Mixes to form hybrid orbital
Which forms a MO with H (1S)
2 more p-orbital available for bonding
Contours & bonding of sp-hybridization
Trigonal Environment: Mixing s & 2-p - sp
2
Contribution from s=0.33; from p=0.66

1
2
2
1 2
0.
3
3
1 1 1
3 2 6
1 1 1
3 2 6
x y
x y
x y
s p p
tr
s p p
tr
s p p
tr



= + +
= +
=
30
30
How do we calculate the coefficients?
Use orthogonality of hybrid orbitals and normalization conditions
There is no unique combination/solution
Hybridization of s & 3-p:sp
3
: Tetrahedral
Contribution from s=0.25; from p=0.75
No p-orbital available
1
2
2
2

1 3
0. 0.
2 2
1 2 1
0.
2 3 2 3
1 1 1 1
2 6 2 2 3
1 1 1 1
2 6 2 2 3
y
tr
tr p
tr
tr
x y z
x z
x y z
x y z
s p p p
s p p
s p p p
s p p p




= + + +
= + +
= +
=
Hybridization of s,p,d: sp
3
d
2
and sp
3
d
Similarly, sp
3
d
trigonal bipyramidal
Sp
3
d
2
: octahedral
Visualizing Pentacene with
Atomic Force Microscopy
AFM Image of Pentacene: Science August 30, 2009
Collaboration of engineers and scientists
as led to such fantastic discoveries