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CHEM F111 : General Chemistry
1
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General Chemistry (Overview of handout)

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Quantum theory
Conformation
Atomic structure and spectra Stereochemistry
Chemical bonding
Types of reactions:
Elimination
Spectroscopy:
Addition
Substitution
Pericyclic
Vibrational
Electronic
NMR
Chemical thermodynamics Aromatic compounds

Chemical Kinetics
Coordination compounds
Octahedral
Tetrahedral
Square planar geometries
2
Books
Text Books
T1: Elements of Physical Chemistry: 6th Edition, Oxford
University Press, Oxford, reprinted in 2015, P.W. Atkins and Julio
de Paula,
T2: Organic Chemistry, 10th Edition, John Wiley & Sons, Inc. New
York, 2011, T. W. Graham Solomons and Craig B. Fryhle,
Reference Books:
R1: Physical Chemistry, David Ball
R2: Concise Inorganic Chemistry, 5th Edition, Blackwell Science,
Oxford, 1999, J. D. Lee,
R3: Inorganic Chemistry: Principles of Structure and Reactivity,
4th Edition, Huheey, Keiter
R4: Organic Chemistry, 6th Edition, PHI, New Delhi, 1992, R. T.
Morrison and R. Boyd,
General Chemistry (Evaluation components)

Component Duration Weightage Date and Time
(%)
Remarks
Mid- 90 min.
Semester
test
Tutorials 10 min.
30
Closed
book
Compre. 3 hours
Exam.
45
Will be
announced
by ID
Continuous
25
Closed
book
02/12 AN Partially
open book
Tutorial: Evaluation components

Tutorial Hour
Clarification of doubts
Further discussion and interactions
Problem solving
Periodical and continuous evaluation: Two types: 10 min.
Quiz: A set of objective type questions (different types), which
the student will have to answer and submit during the tutorial
class.
Assignment: A set of problems will be assigned periodically, of
which one to be solved in the tutorial hour of the following week.
Assignment/Lecture slides/Notices will be uploaded on

the Nalanda (upon activation).
Please register yourself on Nalanda
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chemistry website:
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CLASSROOM RULES
Quantum Theory: Background

Classical Mechanics:
Describes the motion of macroscopic objects,
from pendulum, projectiles to parts
of machinery, as well as astronomical objects,
such as spacecraft, planets, stars, and galaxies.
Galileo
Euler
Newton Laws of motion
Lagrange
Hamilton
unaltered for three centuries till end of 19th Century
8
Classical Mechanics: Consequences

1. Predict a precise trajectory for particles with precisely
specified locations and momenta at each instant.
2. Any kind of motion can be excited to any arbitrary value
of the energy
3. Waves and Particles are distinct concepts
Certain Phenomena were unexplainable ???

? Black body radiation
? Photoelectric effect
? Electron diffraction
? Line spectra of atoms
.Foundation of Quantum Mechanics
9
Black body
Study of Interaction of light with matter was in progress.
(How light was emitted or absorbed ??)
Any object radiates energy, when heated. The amount of
energy emitted, and its frequency distribution depends on
the temperature and on the material.
Black Body: A perfect absorber and a perfect emitter:

Theoretically it can be approximated as a small hollow
cavity with a tiny hole for light to escape.
Actual black bodies don't exist in nature

10
Black body radiation-the phenomena
At constant T, Intensity increases as

increases, attains a maximum value and
then decreases.
Not all the wavelengths of light are
emitted equally.
11
Intensity (I) or
Power density
Such solid black bodies, when heated to glowing emitted a

continuous spectrum composed of all wavelengths of light,
called Black Body/cavity radiations.
The distribution of absorbed or emitted radiation depends
on the absolute temperature, not on the body material.
?
Wavelength
Observations: Two Radiations Law

With increase in T, the max shifts
towards shorter wavelength.
max T = b
b = 2.9 mmK
[Wiens Displacement Law]
(, T) increases with increase in T.

Area under the curve at T = Total Power per unit surface area (M)
M is proportional to 4th power of absolute temperature and is
proportional to Energy density.
Used to estimate the
M = T4 = ( (, T) d
(W/m2)
= 5.6697 x 10-8 Wm-2K-4 temperature of Sun and
Earth
[Stefan-Boltzmann Law]
12
Blackbody Radiation: Explanation

I. Rayleigh-Jeans Explanation (1900-1905)
attempts to describe the emission spectrum from a black
body at a given temperature through classical arguments.
Assumptions:
Black body cavity is made up of charged particles which behaves
as tiny oscillators by thermal accelerations and emit radiations.
The electromagnetic field thus generated can be considered as a
collection of waves of all possible frequencies.
Average Kinetic energy of each component (per degree of
freedom) of an oscillator was assumed to be kT based on classical
equipartition principle.
13
Rayleigh-Jeans Law
Energy density associated with radiation of wavelength from to
+d : dE = d = (8kT/4) d ; : Energy Density
Energy density rises without

bound as decreases.
Infinite energy density at
short
wavelengths
or
Oscillators of short wavelength

(UV) are excited even at room
temperature.( UV Catastrophe!)
Quite Successful at long wavelengths.
Rayleigh_Jeans Law predicts an Ultraviolet catastrophe that does not
occur in real.
14
Blackbody Radiation: Explanation

II. Plancks Explanation (1900-1909)
attempts to describe the emission spectrum from a black
body at a given temperature through Quantization
hypothesis.
Crucial Assumption:
An oscillator of frequency cannot
be excited to any arbitrary energy, but
to only to integral multiples of a
fundamental unit or quantum of
energy h; h = 6.626 x 10-34 Js, the
Planck constant.
E=nh i.e. Energy of an oscillator is
quantized
The average energy is different from
that in classical physics.
15
Planck Radiation Distribution Law
dE=d =
(8/4)
d (hc/)
[e(hc/kT)
-1]-1
Average
energy
c is speed of light, k is Boltzmanns constant and h is Plancks constant.
Planck proposed empirical formula

describe the curve of blackbody
radiation
exactly
for
all
wavelengths.
Planck expression reproduces the

experimental distribution with
h = 6.63 x 10 34 Js
16
Planck Law: Success story

Planck's hypothesis: An oscillator cannot be excited unless it
receives an energy of at least h (as this is the minimum amount
of energy an oscillator of frequency may possess above zero).
For high frequency oscillators (large , low ), the amount of
energy h is too large to be supplied by the thermal motion of the
atoms in the walls, and so they are not excited.
dE = (8hc/5) d [e(hc/kT) -1]-1

At small , ehc/kT
(Exponential is large)
faster than 5
Energy density 0 as 0
17
UV Catastrophe
avoided
The Magic of Plancks formula

maxT = hc/5k (constant)
Wiens Law
= (2 5k4/15h3c2)T4 = T4
Stefan Boltzman Law
Differentiate d/d = 0 for

calculating max (at low )
M = ( (, T) d
dE = d = (8/4) (hc/) [e(hc/kT) -1]-1 d

exp (hc/kT) = 1 + hc/kT +1/2(hc/kT)2
For long wavelengths,
when hc/ << kT
Dropping
Rayleigh-Jeans formula
18
Photoelectric Effect
19
Failure of Classical Physics to Explain

The Facts
The Believes
No electrons are ejected if the
frequency of radiation is below a
threshold value characteristic of
the metal.
Electron
emitted
should
depend on intensity and not on
frequency.
Kinetic energy of emitted

electrons varies linearly with the
frequency, and is independent of
light intensity.
K.E. should depend on the

amplitude of the oscillation of the
incident radiation.
For frequencies above the

threshold value, emission of
electrons is instantaneous, no
matter how low the intensity of
the light. (Absence of time lag)
The energy of the incident light

is spread over as a wave front and
some time will be required by an
electron to absorb enough energy to
escape.
20
Photoelectric Effect: Einstein Explanation

Light of frequency may be
considered as a collection of
particles, called photons, each of
energy h.
If the minimum energy required to
remove an electron from the metal
surface is (work function), then if Particle Character of Light
h < , no emission of electrons
occurs.
Threshold frequency 0 given by
= h0
For > 0, Ek = h = h( 0).
1/2mv2 = h = h( 0).
21
BITS Pilani
Pilani Campus

Lecture 2
Summary (Lecture 1)
Classical Mechanics: Failures to explain
Black body radiation (1860):

Plancks Explanation (1901-1909):
Energy quantized.
Photoelectric effect (1887):
Einstein Explanation (1905):
Particle character of light.
Energy Quantized
2
Atomic Spectra: The phenomena

White light gets separated into its component colors after passing
through the prism.
When such a light is passed through hot gas/element, some
wavelength of light gets absorbed, while rest when analyzed
through spectroscope shows a series of characteristics lines at
definite wavelength: LINE SPECTRUM
Each element has its own
characteristics spectrum.
Complicated
elements
spectra
of
Comparatively simple spectra

for hydrogen.
3
Mathematical explanation of Line Spectra of

Hydrogen Atom
Balmer (1885): Explained the lines in the visible region of
Hydrogen.
1
1
1
~
Positions of lines of light, wavenumber, R 2 2
2 n
n = 3, 4, 5. & R: some constant
Lyman (1)
Paschen (3)
Pfund (5)
Brackett (4)
Rydberg:Generalized Formula
1
1
1
~
RH 2 2
n1 n2
n1 and n2 (n2>n1) are positive

integers. (RH = 109737.315 cm-1)
4
Bohrs Explanation: Model of Hydrogenlike Atom

Electron (mass m and charge e) moving in circular orbit of radius r
about nucleus of charge Ze;
mev2/r = Ze2/40r2
Bohr postulated that an electron can revolve around the nucleus only
in certain stable orbits without emitting any electromagnetic radiation.
(Electron must radiate energy, fall into the nucleus) [Classical Concept]
Only those orbits are stable for which the magnitude of

L (orbital angular momentum of the electron) is quantized.
L = mevr = nh/2 =n,
n=1,2,3,
0 h2n2
r
me e 2
quantization of angular momentum

Putting n = 1; r = a0 = 0.529 x 10-10 m;
First Bohr radius
5
Bohrs Explanation on Line Spectra of

Hydrogen Atom
Transition between orbits are
allowed, but only when an
electron absorbs or emit a
photon of energy equal to the
difference between the energy
of the orbits. E h
~
E2 E1
hc
1me v 2
me e 4
e2
En KE V
2 2 2
2
4 0 r
8 0 h n
me e 4 1
1
E E2 E1 2 2 2 2
8 0 h n1 n2
4
1
m
e
1
v~ 2e 3 2 2
8 0 h c n1 n2
The equation
corresponds with the
me e 4
RH 2 3
experimentally
8 0 h c
observed result.
6
Bohrs Model of Hydrogen-like Atom

Orbiting electrons existed in orbits
possessing discrete quantized energies
me e 4
13.6
En ( Hydrogen) 2 2 2
eV
2
8 0 h n
n
Bohr Model can make some approximate

predictions about the emission spectra for
atoms with a single outer-shell electron.
Z 2 me e 4 13.6Z 2
En 2 2 2
eV
2
8 0 h n
n
For example:
Be3+: Z = 4: single electron system
Limitation: Bohr Model cannot be applied to elements with more than
one electron
7
Wave Character of Particles

If light (radiation) can be viewed as a collection of particles,
then can entities (particles) also be seen as waves ?
Davisson-Germer Experiment (1920-1925)

Scattering of electron beam
after interaction with single
crystal of nickel.
Series of bright and dark

fringes
8
de Broglie (1924): Wave-particle duality

Just as light exhibits both wave-like (diffraction), and
particle-like characteristics, so should all material objects.
For light (photon)
E = pc (particle) = hc/ (wave)
p = h/
A particle with linear momentum p, has an associated

matter-wave of wave length ( and mathematical form
sin(2x/).
The Joint wave-particle character of matter and radiations is

called wave-particle duality.
9
Wave-particle duality
The wavelength of the matter wave associated with a
particle should decrease as the particles speed increases
Lower p has a longer ;
Higher p has a shorter
.
Macroscopic objects are so massive that the de Broglie

wavelengths are immeasurably small, even if they travelling
slow.
10
Uncertainty: A natural consequence

of wave-particle duality
A wave of wavelength
- corresponds to a particle with a constant p
-wave is spread through out the space.
-Precise location determination: Impossible.
A particle with fixed position (x)
-associated with wave of the form sin(2x/).
-Localized wavefunction(0) at x and 0 elsewhere.
11
Uncertainty or Indeterminacy!
A
sharply
localized
wavefunction can be generated by
superposition of large no. of
wavefunctions. (resultant wave:
spread of waves of different
wavelengths)
Superposition of many waves

corresponds to superposition of
many different linear momenta.
(which of these wavelength should
fit into de broglie equation to give
momentum)
-Precise momentum determination: Impossible

12
Heisenberg Uncertainty Principle

It is impossible to predict, measure, or know both the exact
position of an object and its exact momentum at the same
time. In fact, an object does not have an exact position and
momentum at the same time! (Contrary to classical Mechanics)
px x /2
px : uncertainty in linear momentum

x : uncertainty in position
(a) (x: large) then (px : small)

(b) (x: small) then (px : large)
Complementary variables, increase in the precision of one

possible only at the cost of a loss of precision in the other.
Trajectories not defined precisely.
13
Quantum Mechanics (QM): Discovery

Black Body Radiation
&
Line spectra of atoms
Atoms/molecules
exist with only
certain energies
De broglie duality
&
uncertainty principle
Davisson-Germer Exp.
&
Particle moving in precise

paths cannot have fixed
speeds.
Wave exhibit particle like

properties &
Particle exhibit wave like
properties
Quantum Mechanics:
A theoretical Science:
A particle is spread through space like wave. To describe this
distribution, a mathematical equation is required.
Wavefunction
14
Wavefunction: / (PSI/psi)
Describing wave behavior of matter (any system) using an
expression of a wave: wavefunction [ ]
In QM, a particle is not localized. Approximately, wavefunction is a
blurred version of path.
At any particular instance of time: should depend upon (x,y,z,t)

(state of a system): time dependent wavefunction
(x,y,z,t) = (x,y,z) f(t)
is time-independent wavefunction, (wavefunction for a stationary
State)
Wavefunction determines the probability distribution of finding

the particle at a point at any instance.
15
Wavefunction: Born Interpretation

It is difficult to establish that a particular particle (electron) is in a
particular space at a particular time. Rather, over a period of time, the
particle has a certain probability (P) of being in a certain region
(between two points a & b).
: Probability Amplitude
2: Probability Density
Probability that the particle is

located in the infinitesimal element
of volume dV about the given point,
at time t = 2dV
Total Probability between a & b =
P=
* dV =
dV
16
Characteristics of Wavefunction:
Only those wavefunctions which follow the following criteria
are considered acceptable wavefunctions:
must be single valued & Bounded (Born Interpretation)
and d/dx must be continuous
all space 2 d must be finite, ie., must be normalizable.
all space
2 d
= 1 or
2 d
=1
(Born Interpretation)
17
Normalization
If the given wavefunction is not normalize: we could make it
normalize by multiplying it by any constant and integrating
over its limits and determine the value of Normalization
constant.
Question: The wavefunction (x)= sin (x/2) for a system exist.

If the region of interest if from x= 0 to x = 1. Normalize the
function.
N (x) (Normalizable)
Solution: (x)(unnormalizable)
Such that
= N2
=1
= N2 [1/2] = 1 ;
Thus, (x)=
N=
sin (x/2) is now Normalizable

18
Observables & Operators

A wavefunction should be defined in such a way that various
observable properties of the system can be determined.
y observable in quantum mechanics is represented by an operator which is use

Each individual property (x, p, E): An observable.
in physical information about the observable from the state function. For
rvable
is represented
in classical
physicsexist
by a function
Q(x,p),instruction)
the correspon
Forthat
every
observable:
an
Operator
(Mathematical

ator is Q( x, p) .
Observable
Operator
Position
Momentum

p
i x
Energy
2
p
2 2
E
V ( x)
V ( x)
2
2m
2m x
19
System Information from

observables
For determining values of observables: perform mathematical
operation (operator) on the wavefunction.
Observable operator acts on a function to give information

about the property
Multiplication operator: M (2,3) = 2 x 3 = 6

Differentiation operator: D [F(x)] = d/dx (9x2+8x) = 18x+8
Momentum of a system = p [F(x)] =
20
[F(x)]
Eigen value Function

Special type of operator-function combination:
Operator when operated on function gives some constant(s)
times the original function: Eigen function of operator
Let the function defining a system be:
Let the operator corresponding to a observable be : A
A =K
K = constant = Eigen Value
is the Eigen function of the operator.

Not all functions are Eigen functions of all operators.
Only those physical properties are determined by function if

that wavefunction is an eigen function of the corresponding
operator.
21
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Lecture 3
Summary (Lecture 2)
Foundation of Quantum Mechanics
Why Quantum Mechanics ?
Wavefunction
Characteristics of an acceptable wavefunction
Single-valued
Continuous & differential

Bounded
Normalized
2
Probability Density is more Informative
Use of Eigen value Function

For determining the value of an observable (property, e.g. p, E)
for a physical system:
-Operate the operator (p, E) on well-behaved wavefunction ()
of that system.
-This operator-function combination should form eigen value
equation and the corresponding eigen value = value of that
observable.
Information about the system could only be known if we know the
eigen value of observable.
A given wavefunction is an eigen function of some operators by not

an eigen function of others.
Not all observables are determined by any one wavefunction.

4
Energy: Hamiltonian Operator

= mv2/2 + V = p2/2m + V
E (total Energy) = KE + PE
Energy Operator : Hamiltonian ( H ) operator

px=
p2
2 d 2
H
..In 1-D
V
V ( x)
2
2m
2m dx
2 2
2
2
2 2 2 V ( x, y, z ) ..In 3-D
Cartesian
2m x y
z
coordinates
2 V
2m
Laplacian operator
Time-independent Schrdinger Eq.

Energy of a system could be known by operating total energy
operator on the wavefunction.
The wavefunction (for stationary states; independent of time)
satisfies the Schrdinger equation:
= E
2 2
2
2
2 2 2 V ( x, y, z ) ( x, y, z ) E ( x, y, z )
y
z
2m x
When is operated upon by , returns the multiplied by E; a

category of equation called eigen (=own) value eqn.
Second order differential equation: the solutions will provide the
energies of possible states
6
Next What ?
? How to extract information from the solutions

? How to solve schrdinger equation for the system
? How to define wavefunction of any system ?

General form of Schrdinger Equation
Acceptable wavefunction
Need for Quantum Mechanics
Application to a Microscopic system

Translation Motion in 1-Dimension: Particle in a Box
Consider a particle of mass m travelling along x-axis,
confined to a length L by infinite potential barriers at x = 0
and x = L (infinitely deep potential well)
V=0
For x < 0 and x > L,

= 0 since
probability of finding
the particle in these
V = regions is zero.
V=
Particle in one-dimension box

Bead free to slide
between two stops
QM: wave associated

with particle
= sin kx or cos kx or
a combination of both
Boundary conditions must be

satisfied by the wavefunctions
Particle in 1-D box: Wavefunction

Let the trial wavefunction be ( x) A sin kx B coskx
Applying the boundary condition at x = 0 and L gives
(0) 0
B cos k 0 0 B 0
( L) 0
A sin kL B cos kL 0
So, we obtain: A sin kL 0

Now A 0; otherwise will be 0 everywhere.
Hence,
sin kL 0, kL n
n 1,2,3,
n cannot be 0
10
Particle in 1-D box: Normalized wavefunction
The wave function for the system will be

n
( x) A sin
x
n 1,2,3,
L
Now, if (x) is normalized wave function then
nx
nx
0 * ( x) ( x)dx ( A sin L ) * ( A sin L )dx 1
0
L
nx
A sin
dx 1
L
0
L
Solution gives A2L/2 =1

or A = (2/L)1/2
2 n
Normalized wave function for particle ( x)
sin
L L
in a 1-D Box
11
Particle in 1-D box: Calculating Energy

( x)
2 n
sin
L L
=E
2 d 2
2 d 2 2
n
(
x
)
sin
2
2m dx 2
2m dx L L
2 n
2mL
2 d n
cos
x
L dx L
h2n2 2
h2n2
n
sin
x
[ ( x)]
2
2
8mL L L
8mL
n2h2
En
8mL2
n = 1, 2,
Quantized energies of the paricle in a 1-D box; n: quantum number

12
Ground State wavefunction and Energy
2 1
1
sin
L L
12 h 2
En 1
2
8mL
2
n h
p
En
2
8mL
2m
h nh
p
2L
2L
If n = 0; then = 0 everywhere and particle

vanishes (Not possible).
The energy at lowest cannot be zero;
consequence of uncertainty principle: particle
is within the box, so uncertainty in position,
x cannot be infinite; px (or energy) cannot
be zero.
Ground state energy: h2/8mL2 :Zero point energy

13
Plot of wavefunctions vs position

= 2L/n; where n = 1,2,3,4
= 2L/3
3
2 3
sin
L L
= L/2
2 1
sin
L L
=L
= 2L
1
2 4
sin
L L
2 2
sin
L L
The wavefunctions are all symmetric or antisymmetric about the

midpoint of the box
14
Probability Amplitude (b) & Density (c)

32 h 2
E3
9 E1
2
8mL
node
22 h 2
E2
4 E1
2
8mL
12 h 2
E1
8mL2
n 1 nodes in n, energy increases with increasing
number of nodes, no nodes in ground state
15
Classical Limit
n2h2
En
8mL2
(i) E depend on L, the size of the system and m,

the mass of the particle.
(ii) Greater the value of L or m, the less important
are the effects of quantization on translational
motion: classical limit
(iii) As n becomes very large, the probability

distribution becomes uniform (continuous)
over the entire length of the box.
At sufficiently high energies, the quantum
mechanics agrees with classical mechanics.
Correspondence principle
16
Particle in two dimensional (2-D) box

A two-dimensional square
well.
Potential energy is zero
between x = 0 and x = L1 and
y= 0 and y = L2,
Rises sharply to infinity at the
walls.
( x, y ) X ( x).Y ( y )
x X(x) = Ex X(x)
y Y(y) = Ey Y(y)
E= Ex + Ey
17
Particle in 2-D box: Schrdinger Equation

2 d 2
d2
2 2 ( x, y ) ( E x E y ) ( x, y )
2m dx
dy
2 d 2
d2
2 2 X ( x)Y ( y ) ( E x E y ) X ( x)Y ( y )
2m dx
dy
On Solving
nx,ny ( x, y) X nx ( x).Yny ( y)
2
nx x
2
X x
sin
L1
L1
..
ny x
2
Y y
sin
L2
L2
..
18
nx h 2
Ex
2
8mL1
2 2
ny h
Ey
2
8mL2
Particle in 2-D box: Wavefunction & Energy

nxx n yy
2 2
sin
( x, y)
sin
L1 L2 L1 L2
2
ny h2
nx h
E
Where nx= 1,2,3.; ny=1,2,3

2
2
8mL1 8mL2
Now, when L1 = L2
(nx n y )h 2
2
8mL2
nx= 1 & ny=1 : Ground state energy of particle in 2-D box (square)
nx= 1, ny=2 & nx= 2, ny=1 : Degenerate Energy level
(Double degenerate states)
19
Particle in 2-D box (square): Wavefunctions

2 , 2 ( x, y )
2 2x 2y
sin
sin
L L L
E2, 2
Non Degenerate state
1, 2 ( x, y )
2 x 2y
sin sin
L L L
2,1 ( x, y )
2 2x y
sin
sin
L L L
E2, 1
E1, 2
Doubly Degenerate states

2-fold degenerate
1,1 ( x, y )
2 x y
sin sin
L L L
E2 , 2
8h 2
8mL2
E1, 2
5h 2
E2,1
8mL2
2h 2
E1,1
2
8
mL
E1, 1
20
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Lecture slide uploaded on
Department of Chemistry
pedagogy
course related
material
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Lecture 4
Summary (Lecture 3)
Application of Quantum Mechanics
to a Microscopic system
General form of Schrdinger Equation
Translation Motion in 1-Dimension

Translation Motion in 2-Dimension
A real example: Numerical

Question: -carotene play an important role in the chemistry of
mammalian vision. If the approximate length of the 1D-molecular box
in -carotene is L = 3.08 nm. Estimate the wavelength of light
absorbed by this molecule from n=11 to n=12.
L = 3.08 nm
2
h2
h
2
2
2
2
Solution: E E12 E11
n
12
11
12
11
8mL2
8m(3.08 x10 9 ) 2
A real example:
Question: -carotene is a linear polyene in which 10 single and 11 double
bonds alternate along a chain of 22 carbon atoms, if we take each CC bond
length to 140 pm, then the length of molecular box in -carotene is L = 3.08
nm. Estimate the wavelength of light absorbed by this molecule from its
ground state to the next-higher excited state.
Solution:
h2
2
2
E E12 E11
n
n
12
11
8mL2
Particle in three dimensional (3-D) box
( x, y, z ) X ( x).Y ( y ).Z ( z )
x X(x) = Ex X(x)
E= Ex + Ey + Ez
y Y(y) = Ey Y(y)
z Z(z) = Ez Z(z)
= x + y + z
[X(x) Y(y) Z(z)] = {x + y + z} [X(x) Y(y) Z(z)] = (Ex + Ey + Ez ) [X(x) Y(y) Z(z)]
2 2
2
2
2 2 2 X ( x)Y ( y ) Z ( z ) ( E x E y E z ) X ( x)Y ( y ) Z ( z )
2m x
y
z
5
Particle in three dimensional (3-D) box

Acceptable solution:
nx,ny ,nz ( x, y, z ) X nx ( x).Yny ( y)Z nz ( z )
2 2
nx,ny ,nz ( x, y, z )
L1 L2
2
nxx n yy nzz
2
sin
sin
sin
L3
L1 L2 L3
2
ny h2
nx h
nz h 2
E
2
2
2
8mL1 8mL2 8mL3
(nx n y nz )h 2
2
If L1 = L2 = L3 = L (cube):
8
nxx n yy nzz
sin
nx,ny ,nz ( x, y, z ) 3 sin
sin
L
L L L
6
8mL2
Particle in 3-D box (cube): Energy Levels

E3,3,3 E5,1,1 E1,5,1 E1,1,5

E1, 1,3
E1, 3,1
27 h 2
8mL2
E2, 2, 2
E3, 1, 1
Accidental Degeneracy
E2 , 2 , 2
E1,1,3
Triply Degenerate states

E1, 2,2
E2, 2,1
E2, 1, 2
12 h 2
8mL2
11h 2
E1,3,1 E3,1,1
8mL2
E1, 2, 2 E2, 2,1 E2,1, 2

E1, 1,2
E2, 1,1
E1, 2,1

8
x y z
1,1,1 ( x, y, z ) 3 sin sin sin
L
L L L
E1, 1, 1

7
E1,1, 2
9h 2
8mL2
6h 2
E1, 2,1 E2,1,1
8mL2
3h 2
E1,1,1
8mL2
Orthogonality & Normality of Wavefunctions

all space m*m d = 1
Normalization
all space m*n d = 0 (if m n) Orthogonality

All wavefunctions of a system are orthogonal to each other.
Orthonormality
all space
* d
m
n
{
8
0 if m n
1 if m = n
Average value of Observables

If the wavefunctions are not the eigen functions of some operator,
then:
1. Exact/specific values of observables cannot be determined for any
state.
2. However, we could still determine the average value of observables,
which provide us some information about the system.
b
d
Average value of observable A= A *A
If is normalized
a
Average value of observable A= A

If is not normalized
*A d
a
b
*d
a
For e.g., The wavefunctions of particle in a box are not eigenfunctions of the
position and momentum operator, such that their average values can be
calculated.
9
Average value of Position for particle in a box

Question: Determine the average value of position of an electron having
the lowest energy level (n = 1) in a particle-in-a-box (x=0 to a)
Solution: Wavefunction for lowest level of particle-in-a-box:
2 n
( x)
sin
x
L L
For determining position, we require position operator:
x ( x) ( P) ( x)
The wavefunctions is not eigenfunction of the position operator.

a
Average value of observable position= x *xdx

a
2
2 x
xa
2x a
2x
a
2 x
x x. sin
dx
sin
2 cos

a0
a
a 4 4
a 8
a 0 2
a
10
Vibrational motion: Classical Mechanics

Turning point; K.E = 0; V= max.
One-Dimensional displacement x from

equilibrium position
Force acting against the displacement x;
Hookess Law: F = -kx
kx2
V ( x) Fdx (kx)dx
2
x can take on any value. Energy is
continuous, continuous range of values.
Parabolic Potential Energy
x = 0; V = min. (0); K.E = max.

11
Vibrational motion: Quantum Mechanics

A wavefunction for a one-dimensional harmonic oscillator can be
represented by time-independent Schrdinger equation:
=E
2
2
d
1 2
kx
2
2m d x 2
kinetic energy
potential energy
2 d 2 1 2
kx E
2
2
2m d x
Solve the Schrodinger equation and apply the boundary conditions

(Boundary conditions: as x ): (Solution not in syllabus)
12
Quantum Mechanical Solution of

Harmonic Oscillator
1
4
Wavefunction
n N n H n x e
x 2
x 2 2
0 .e

1
4
x 2

1 . 2 .x . e 2

n 0,1,2,...
4 2m
Nv
: Normalization constant
Normalization
constant
: Vibrational quantum No.
Hv :
Hermite Polynomials
Hermite Polynomials
Vibrational frequency
1
2
1/ 2
k

m
13
1
4
1
x 2 2
2
2x 1. e
.
2
Quantum Mechanical Harmonic Oscillator

Wavefunction
The normalized wavefunction and probability distribution (shown also by

shading) for the lowest energy state and first excited state of a harmonic
oscillator.
14

Total Energy: Eigen value
Energy of the oscillator:
1
En n h ; n 0,1,2,...
2
n vibrational quantum number

Force constant k
Particle mass m
Evenly spaced energy levels.
Spacing h
1
Ground state energy: E0 h

2
2
(Zero point energy)
Atoms in a solid lattice or in polyatomic molecules cannot have zero energy
even at absolute zero temperature. "zero point vibration".
15

Wavefunction
Number of nodes is n.
Wavefunctions alternately symmetric or antisymmetric about x=0
16

The Probability Distributions
Regions of highest probability move towards the
turning points: Correspondence to classical
mechanics.
As n increases, probability that the particle is in the
centre of the energy well decreases and the
probability of its being at the sides of the potential
well increases.
n becomes large, probability distribution resembles
the classical result.
wavefunction extends into classically

forbidden region. (Tunneling)
17
Notice
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pedagogy
course related
material
On Nalanda
http://nalanda.bits-pilani.ac.in
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Find the course CHEM F111
Assignment 1 will be conducted in your tutorial sections
between 17-22nd August
BITS Pilani
Pilani Campus

Lecture 5
Summary (Lecture 4)
Simplest Application of Quantum Mechanics
Translation Motion in 3-Dimension: Energy &

Wavefunction
Orthogonality
Average value of an obsevable
Harmonic Oscillator: Energy & Wavefunction
Rotation in 2-D: particle on a ring

Angular
momentum: Lz (Jz) = pr
Particle constrained to move on a ring of radius r.

Entire energy is kinetic.
The potential energy is constant and can be taken
to be zero (as it is unchanged during rotation).
V = 0 (assumption)
3
Particle on a ring: Quantum Mechanical aspect
Consider a particle of mass m moving in a circular path of radius

r (2-Dimension) such that it form an angle (with x-axis)
= KE + PE = p2/2m + 0
Lz = pr
2 d 2
d2
2 2 ( x, y) E ( x, y)
2m dx dy
.. Cartesian coordinates
The wavefunction may be better treated in terms of angle ()
= p2/2m = Lz2/2mr2 = Lz2 /2I
( x, y)
L i x y i
z
y x
( )
4
Particle on a ring: Schrodinger Equation

2 d 2 ( )
E ( )
2
2I
d
.. Second order differential equation
Solve the Schrodinger equation and apply the boundary conditions

(Solution not in syllabus)
Wavefunction should be a periodically varying function

Cyclic Boundary conditions:
() = (2 + ):
The wavelength should
fit to the circumference
2r of the circle.
m = 2r
m = 0, .
5
Particle on a ring: Wavefunction

2 d 2 ( )
Solving
)
2I
d 2
Acceptable Wavefunction
m ( ) Ae im
Normalization
2
im
im
A
(
e
)
*
A
(
e
)d 1
im
im
A
(
e
)
A
(
e
)d 1
Normalized Wavefunction:
0
2
2
A
d 1
im
e
m ( )
1/ 2
2
1
A
2
6
Particle on a ring: Energy

2 2 ( ) 2 2 eim
1/ 2
2
2
2I
2 I 2
m 2 2
( )
2I
Energy level
Quantized
L2z m 2 2
E
2I
2I
m (or ml) = 0, .
Degeneracy: All levels with ml 0 are

doubly degenerate i.e., there are two
states of the same energy. The two
states differ in the sense of rotation.
No zero point energy. with ml = 0 ;
Ground state nondegenerate.
7
Particle on a ring: Wavefunctions

e 2i
2 ( )
2 1/ 2
eiml
ml ( )
2 1/ 2
ml = 0, .
e 1i
1 ( )
2 1/ 2
0 ( )
1/ 2
Particle on a ring: Momentum Lz
Lz ml m 1 eim
i
i 2 1/ 2
Angular momentum
1
iml
iml
e ml ml
Lz is Quantized
1/ 2
i 2
l
The solutions of the Schrdinger

equation,
eigenfunctions
of
the
Hamiltonian
operator,
are
also
eigenfunctions
of
the
angular
momentum operator Lz
H and Lz are commutable: the
energy and the angular momentum can
be known simultaneously.
9
Rotation in three dimensions

Rotational motion in three dimensions could be a mimic of
electrons around nuclei in atoms. (except that particle here is at fixed
distance r )
Thus, a particle could be considered as if moving on the surface of a
V=0
sphere.
(particle confined to a spherical space)
Two angles
- the azimuthal angle
z
- the colatitude
x, y, z ,
Motion of a particle over sphere is like

motion of particle over a stack of rings, with
additional freedom to migrate between rings.
x
10
Hamiltonian operator in polar coordinates
H
2 V
2m
2
2
2
2
2 ..
2
y
z
x
2
Cartesian coordinates
2
2
1
1
2
sin

2
2 2
2
r
r
r
sin
sin
Legendrian Operator
11
2
Hamiltonian operator in polar coordinates

2
2
1
1
2
sin

2
2 2
2
r
r
r
sin
sin
Since r is fixed
1
2
2
r
1
2
1

sin
2
2
sin

sin
.. polar coordinates
1 2
2
r
12
The Schrdinger equation:

Particle on a sphere rigid rotor
The Schrdinger equation:
=E
2 V E
2m
2
2 1 2
2 , E ,
2m r
r constant
V=0
I = mr2
1 2
2
r
2
E
2I
2
2
2I
1
2
1

sin
E
2
2
sin

sin
.. Schrodinger equation in polar coordinates
13
Particle on a sphere rigid rotor:

Schrdinger Equation
2
2I
1
2
1

sin
E
2
2
sin

sin
1
2
1

2 IE
sin

2

2
2
sin

sin
2
sin
Multiplying by
& rearranging

1 2 sin
2 IE 2
sin
2 sin 0
Depend on
Depend on
Solving the Schrodinger equation and applying the appropriate
cyclic boundary conditions
14

wavefunction
The solution of the equation involves the polar angle and the
azimuthal angle as variables. The solution is complicated.
Imposing first boundary condition emphasis that the acceptable
wavefunction must be described as the particle travel round the
equator (similar to particle in a ring)
Such that = 0 to 2 and the acceptable solution for the above
boundary condition should introduce a quantum number, ml
Imposing second boundary condition emphasis that the acceptable
wavefunction must be described as the particle travel across the
poles.
Such that ( = 0 to ); This constraints introduces a second quantum
number l called orbital momentum quantum number.
15

Acceptable solution of wavefunction
The acceptable solution of wavefunction:
Spherical harmonics = Yl,ml( , ) = l,ml( )ml()
iml
such that
e
Polynomiall ,ml ( ).
1/ 2
2
l = 0,1,2...
For a given value of l there are 2l+1 permitted values of the
magnetic quantum no. ml.
ml = l, l-1,,- l
16

Acceptable solution of wavefunction
Yl,ml could be imagined as wave like distortions on a

spherical shell.
l
ml Yl,ml( , )
0
1
0
1
2
17
Particle on a sphere
Energy & Momentum
rigid
rotor:
The solution of Schrodinger eq. also gives the energy, E of the

particle restricted to the values:
Energy = l(l + 1)2/2I
l = 0,1,2,3.
Energy is quantized and is independent of ml.
A level with quantum no. l is (2l+1) fold degenerate.

Degeneracy = (2l+1)
Classically, E = L2/2mr2
(Particle constrained to rotate on surface of sphere of radius r)
Comparing we get
L = [l(l + 1)]1/2
Total Angular momentum is Quantized

18
Lz: z component of angular momentum

particle on a sphere rigid-rotor
z-component of the angular momentum,
Lz = ml
where as for a given l, ml may take on one of the 2l+1
values -l, -(l+1),...0,..., l-1, l
In other words, the angular momentum vector may only
make one out of a discrete set of 2l+1 angles with any
chosen axis in space, say the z-axis
Two aspects of the quantization of angular momentum
vector, the magnitude and its orientation
Lx and Ly could not be known.
19
BITS Pilani
Pilani Campus

Lecture 6
Summary (Lecture 5)
Particle on a circle: Energy & Wavefunction

Particle on a sphere: Energy & Wavefunction

wavefunction & Energy
The acceptable solution of wavefunction:
iml
such that
e
Polynomiall ,ml ( ).
1/ 2
2
l = 0,1,2...
For a given value of l there are 2l+1 permitted values of the
magnetic quantum no. ml.
ml = l, l-1,,- l
Energy = l(l + 1)2/2I

3
Particle
L & Lz
on
sphere
L = [l(l + 1)]1/2
rigid
rotor:
Total Angular momentum is Quantized

L Lx Ly Lz
The angular momentum vector (L) may only make one out
of a discrete set of 2l+1 angles with any chosen axis in space,
say the z-axis.
z-component of the angular momentum,
Lz = ml
where as for a given l, ml may take on one of the 2l+1
values l, l-1,,- l
Lx & Ly cannot be determined.
4
Space Quantization -
Lz
Two aspects of the quantization of

angular momentum vector (L),
the magnitude and its orientation.
For each l, there could be limited ml
values,
the orientation of a rotating body is
quantized.
For a particle having a certain energy
(e.g. characterized by l=2), the plane
of rotation can only take a discrete
range of orientations (characterized
by one of the 2l+1 values ml)
Space quantization
5
Vector model of angular momentum Lz
Case l = 2, ml = 2, 1, 0, -1, -2
Space Quantization -
Lz
l=1
ml = 1, 0, -1
Hydrogen
& Hydrogen like atoms
Hydrogen Atom
Atom = 1 electron (me) and 1 nucleus of mass mN.
The atom is a 2-body system: both the nucleus and e- move with
respect to each other (relative motion) and both move with respect
to an outside reference point (motion of the centre of mass).
Because of the electron charge and the positive charge |Ze| of the
nucleus, the potential energy V(r) has to be taken into account in the
energetics of the system.
2
Note that the potential is
Ze
V(r)= spherically symmetric, i.e., it
4 0 r
depends only on the distance r
Since mn >> me, the nucleus may be taken to be at rest, and the
electron moving about it.
9
Hydrogen-Like Atom: Hamiltonian

The Hamiltonian for internal motion of the electron relative to the
nucleus is
2
2
2
2
2
V (r )
H
2
2
2 x y
y
mn me
mn me
2
2
2
1
1
sin
V (r )
H
2 2
2
2
2 r
r r r sin
sin

.. Hamiltonian operator in polar coordinates

2
2
2
1 2
2
H
2 V (r )
2 r
r r r
10
Hydrogen-Like Atom: Schrdinger Eq.
H (r , , ) E (r , , )
(r , , ) R(r ) R(r ) Y ( , )
2 2 2
1 2
2
2 V (r )[ R(r ) ] E[ R(r ) ]
r r r
2 r
2 2 2
1 2
2
2 V (r )[ R(r )Y ( , )] E[ R(r )Y ( , )]
r r r
2 r
Rearranging terms
2 2 2 R( r )
R(r )
2
2
2
2
r
2
r
V
r
E
r
Y ( , ) 0
2
2R
r
r
2Y ( , )
Depend on &
Depend on r
11
Hydrogen-Like
conditions
Atom:
Boundary
2 2 2 R( r )
R(r )
2
2
2
2
r
2
r
V
r
E
r
Y ( , ) 0
2
2R
r
r
2Y ( , )
Solving the Schrodinger equation and applying the appropriate

boundary conditions:
r = 0 to
= 0 to 2
= 0 to
n ,l ,m (r , , ) Rn ,l (r )l ,m m Rn ,l (r ) Yl ,m ( , )
l
Such that:
n = 1,2,3..
l<n
Radial part of
wavefunction
ml l
12
Angular part of
wavefunction
Hydrogen-Like
Solution
Atom:
Angular
The angular part of the solution is the same for a particle in any
spherically symmetric potential.
iml
Yl,ml( , )
e
Nl ,ml polynomiall ,ml ( ).
1/ 2
2
Normalization constant
The magnitude of angular

momentum (L): = l(l + 1)]1/2
l can take on the values 0,1,2,3,...
Associated Legendrian polynomial
z-component of angular
momentum (Lz) = ml
(2l+1) values of ml
with ml = l, l-1,,-l
The angular momentum vector (L) may make only a discrete set of 2l+1
angles with any chosen axis in space, say the z-axis.
13
Hydrogen-Like Atom: Angular Solution
ml
Spherical Harmonics
0
1
2
Source: google
14
Hydrogen-Like Atom: Radial Solution

The acceptable solutions can be found only for integral values of a
quantum number n,
2 Zr
Rn,l (r ) N n,l polynomialn,l ( ) e 2 n

n
l
a0
4 0 2
a0
me e 2
Normalization constant
A term in (or r) of degree l
polynomial in (or r) of degree n-l-1

Associated Laguerre polynomial
n = 1, 2, 3, ......
l = 0,1(n-1)
15
Radial Solution: Physical significance
Rn,l (r ) N n,l polynomialn,l ( ) e 2 n

n
l
n could be
determined
the function goes

to 0 as r
Behavior at r = 0
(only l = 0 wavefunctions are
polynomial in (or r) of degree n-l-1
nonzero at the origin)
:the number of radial nodes (n-l-1)
16
Hydrogenic Radial Wavefunctions

R1, 0 ( r )
n =1
Z
2
a
0
3/2
l =0
e /2
No. of radial nodes (n-l-1) = 0
R2 , 0 ( r )
n =2
l =0
R2 ,1 ( r )
n =2
=1
Z
1
1/2 a0
4 6
3/2
Z
1
1/2
2 2 a0
3/2
1 /4
2 e
2
e /4

17
Hydrogenic Radial Wavefunctions

R3, 0 ( r )
1 Z
1/2
9 3 a0
n =3
=0
3/2
1 2 /6
6 2 e
9
R3,1 ( r )
Z
1
1/2 a0
27 6
3/2
1 /6
4
n =3
l = 1 No. of radial nodes (n-l-1) = 1
R3, 2 ( r )
n =3
=2
1/2 a0
81 30
3/2
2e /6

18
Hydrogen-Like Atom: Wavefunction
n,l ,m (r, , ) Rn,l (r) Yl ,m ( , )

l
im
e
n,l ,ml (r , , ) N n,l ,ml . . polynomialn,l ( ). e 2n . polynomiall ,ml ( ).
2
n
n = 1,2,.;
l = 0,1,.(n-1);
ml = -l,.+l
The wavefunction (r, , ) of the electron in the hydrogenic atom

is called an atomic orbital. An orbital is a one-electron
wavefunction.
Electron described by a particular orbital is said to occupy that
orbital.
19
Hydrogen-Like Atom: Wavefunction

Atomic orbitals specified by three quantum numbers n, l, and ml
The maximum number of physical quantities
simultaneously be precisely specified is three,
Energy
that
can
n (principal quantum no.)
Angular momentum
One of the spatial components

of Angular momentum
l (Orbital angular momentum

quantum no.)
ml (Magnetic quantum no.)

20
BITS Pilani
Pilani Campus

Lecture 7
Summary (Lecture 6)
Particle on a sphere:
Energy
Wavefunction
Angular momentum L
Hydrogen & Hydrogenic Atom:
Angular solution
Radial solution
2
Hydrogen-Like Atom: Solution
n ,l ,m (r , , ) Rn ,l (r ) Yl ,m ( , )
l
Such that:
Radial part of
wavefunction
n = 1,2,3..
l<n
ml l
Angular part of
wavefunction
im
n,l ,ml (r , , ) N n,l ,ml . . polynomialn,l ( ). e 2n . polynomiall ,ml ( ).

2
n
l
The wavefunction (r, , ) of the electron in the hydrogenic atom

is called an atomic orbital. An orbital is a one-electron
wavefunction.
3
Quantum Numbers Shell, Subshell, Orbital

Principal quantum numbers, n
Orbital angular momentum

quantum number or Azimuthal
Principal
quantum
number quantum number, l (Subshells)
symbolized as n is the first
Only certain discrete amounts of
quantum number of an atomic
angular momentum are allowed: l
orbital. Labels the energy levels.
l = 0 (s), 1 (p), 2 (d), 3 (f).n-1
n = 1 (K), 2 (L), 3(M)..
Orbital angular momentum, L
(Magnitude)= [l(l+1)]1/2
Magnetic quantum number, ml
Refers, to the direction of the angular momentum vector (around any
arbitrary axis passing through the nucleus): Space Quantization
ml = +l..-l
Each subshell contains 2l+1 individual orbitals.
l = 0 & ml = 0: s-orbital;
l = 1 & ml = +1, 0, -1 : three p-orbitals

4
Atomic orbital
Associated
Atomic orbital is a
Laguerre
one-electron
= polynomials
wavefunction
multiplied by an
defined
by
3
exponential,
and
quantum numbers
characterized by n
(n, l, ml)
and l
Spherical
harmonics
specified with
l and ml
Atomic Orbital represented by : nlml

n: numerals (1,2,);
l: (letters) 0 = s; 1= p; 2 = d; 3 = f.
ml = +l-l
Eg.: if n=3 and l = 2 and ml (5 values) = 2,1,0,-1,-2
3d2, 3d1, 3d0 , 3d-1 , 3d-2 orbitals
5
Shells and subshells

ml |l |
In hydrogenic atoms, all orbitals in the same shell have the

same energy (characterized by n). NB: In many-electron
atoms, well see that the subshells have different energies.
ml
Number of orbitals
with different ml
l (n-1)
n=
l=
1
K
0
s
2
L
1
p
3
M
4
N
2
d
3
f
n
How many orbitals for a given n ? n2
Hydrogen-Like Atom: Eigen Value:

Energy
The energy levels are
En = e4Z2/32n2
n = 1,2,3,.
(Energy depends only on n)

En = - hcRZ2/n2
hcR = e4/32
= mmN/(m+mN)
n=2, Z=1
Constant R is numerically same

as Rydberg contant, RH when
mN is set equal to the mass of proton.
n=1, Z=1
Ground state is stable than infinitely

separated electron and nucleus.
7
Energy levels & Ionization energies

En = hcRZ2/n2
The energies given by the formula are negative, they correspond to a bound
state of the electron.
The zero energy, reference level (n = ) for the energy, corresponds to a
situation where the electron is not bound.
The positive energies correspond to unbound states of the electron. The
wavefunction describing such an electron is also solution of the SE, and it is the
wavefunction of a free electron. The energy of the unbound electron are not
quantized and form the continuum states of the atom.
The ionization energy I, of an atom is the minimum energy required to
remove an electron from the atom that is in its ground state (the state of lowest
energy of the atom).
e.g: For H, there is one electron. The atom is in its ground state when the
electron is in the state characterized by n=1.
I= -En=1 = hcRH = 2.179 10-18J= 13.6 eV
8
Principal quantum numbers, n: Energy Levels

Spectroscopy measures the
changes in energy between two
states.
E = hcR/n22 (- hcR/n21)
= h
-
= R[(1/n12) (1/n22)]
Ground state of hydrogenic atom

Ground State: n = 1, l = 0, ml = 0 1s orbital
1,0,0 = (4-1/2 (4/a03)1/2 e-r/a0 = (1/a031/2 e-r/a0
(independent of and , true of all s states since Y00 = (4-1/2 ).
All s orbitals are
spherically symmetrical, related to their being

states of zero angular momentum.
Probability density depends only on r

Maximum at r = 0, the nucleus: Most probable point at which electron
will be found is at nucleus.
Decays exponentially with distance r
No nodes
Function above is normalized.
10
1s wavefunction and probability density
Radial wavefunction
11
1s wavefunction and probability density

What is the probability that an electron in the 1s orbital of hydrogen
will be within a radius of 2 from the nucleus?
b
P d
Z
2
a
0
3/2
1/ 2
1
e /2
For hydrogen atom, this becomes the three dimensional expression

2 A 2
*r 2 dr sin dd
0 0 0
1
3
a
2A
d. sin d . r e
0
2 2r / a
d r 2 dr sin dd
dr
P = 0.981
12
1s Wavefunction
For all values of & , there is a very small volume near the
nucleus and probability of electron existing in such a small volume
should be small.
Electron probability should not be considered along a straight line

out from nucleus.
13
1s radial distribution function
Volume of spherical shell = 4r2dr
Electron probability should be considered on a spherical surface

around the nucleus.
Probability that the electron will be found in this spherical shell is
=(Prob. density at the radius r) x (volume of spherical shell)
= 2 4r2 dr = p(r)dr
; P(r) = 4r22
Radial distribution function, P(r): gives the probability of finding the
electron in a spherical shell of thickness dr (between r and r+dr) at the
radius r from the nucleus, regardless of the angle/direction.
14
1s radial distribution function Plot

For the 1s orbital, 1s = (1/a031/2 e-r/a0
Therefore, P(r) = 4r2 21s
= 4r2 [(1/a031/2 e-r/a0]2

P(r) = (4/a03) r2 e-2r/a0.
P(r) = 0 at r = 0
P(r) 0 as r
The probability starts at zero, increases to a maximum value, then decreases
toward zero as the radius gets larger and larger.
The most probable radius is the radius at which P(r) is maximum.
At most probable radius, dP(r)/dr = 0
For a 1s orbital in hydrogen, P(r) is maximum at r = a0 (Bohr radius).
15
2s radial distribution function Plot

Spherically symmetric, angular part is just a constant States of zero
orbital angular momentum.
R2 , 0 ( r )
1 Z
1/2
2 2 a0
3/2
1 /4
2 e
2
= 2Zr/ao
For calculating the position of radial node:

At radial node, (2 /2) = 0. Therefore, the radial node is at r = 2ao/Z
P(r) = 4r2 22s
At most probable radius, dP(r)/dr = 0

For 2s orbital in H-atom, most probable radius is 5.2ao
16
Radial Wavefunction
2,0,0 = (1/ (32)) (Z/a)3/2 (2 - Zr/a) e-Zr/2a
1,0,0 = (1/ ) (Z/a)3/2 e-Zr/a
3,0,0 = 1/(81(3)) (Z/a)3/2 (27 - 18(Zr/a) + 2(Zr/a)2) e-Zr/3a
17
17
Radial Distribution Plot (P(r) vs r)

P(r) = Radial
Distribution
Function
Locate the
maxima for
finding the most
probable radius
dP(r)/dr = 0
Find rmax.
18
18
Radial distribution function P(r) for orbitals

that are not spherically symmetrical:
Probability of finding the electron in an
infinitesimal volume element d located at a
distance between r and r+dr from nucleus, with its
angular coordinates having values between and
+d and between and + d is
* d = [Rn,l(r)]2 [Yl,ml(,)]2r2 dr sin dd

The Probability of finding the electron between r and r+dr from the
nucleus, regardless of angle ( and ) can be obtained by integrating over
and is
2
Rn,l(r)]2 [Yl,ml(,)]2 r2 dr sin dd
0
19
Radial distribution function P(r) for orbitals

that are not spherically symmetrical:
2
Probability = P(r)dr = r2 Rn,l(r)]2 dr
[Yl,ml(,)]2 sin dd
Integral of [Yl,ml(,)]2 can be normalized to unity (1)
Therefore, Probability, P(r)dr = r2 [Rn,l(r)]2 dr

Radial distribution function, P(r) = r2 [Rn,l(r)]2
20
Radial wavefunction & Radial

Distribution Plots (P(r) or r2R2 vs. r)
2p
3d
3p
21
BITS Pilani
Pilani Campus

Lecture 8
Summary (Lecture 7)
Angular solution & Radial solution
Plot of Radial wavefunction [R(r)] vs r:
-to determine the position of radial node

-Calculate the position of radial node by putting
polynomial in r (or ) = 0
Radial Distribution function P(r) vs r
for l = 0: P(r) = 4r22
for l 0; P(r) = r2 [R]2
-to determine the Most Probable Radius:
by putting dP(r)/dr = 0
2
2pz Orbital : Wavefunction n=2; l=1; ml = 0
2,1,0 R2,1 (r ) Y1,0 ( , )
Z
1
1/2 a0
4 6
3/2
e /4
1/ 2
3
4
cos
n = 2, l = 1, ml = 0
No. of nodes (n-1) = 1
In spherical polar coordinates
z = r cos
These orbitals have maximum probability density oriented along zdirection.

At r = 0, wavefunction is zero.
The wavefunction is also zero everywhere on the x-y plane
(cos = 0 when = 90o). Nodal plane (1, xy-plane)
The power (l) on r (or ) or power of term = No of
angular nodes =1
These represents atomic states for which energy and
magnitude of the orbital angular momentum can be exactly
known.
3
2p Orbitals : Wavefunction n=2; l=1; ml = 1

2 p R2,1 (r ) Y1,1 ( , )
1
2 p R2,1 (r ) Y1,1 ( , )
1
n = 2, l = 1, ml = 1 or -1
i
1
Z
e /4 sin e
1/2 a0
8
4 6
1
3/2
i
1
/4
sin
e
Z
e
8
1/2 a0
4 6
3/2
These wavefunction contains a imaginary exponential part, thus the

overall wavefunction is a complex function.
The maximum probability density of these orbitals is oriented off-the

z-axis, but along which direction(s), cannot be determined.
These orbitals do not provide the information of properties that are
strongly responsive to orientation in three dimensional space.
4
2p Orbitals : Wavefunction n=2; l=1; ml = 1

2 p R2,1 (r ) Y1,1 ( , )
Z
1
1/2 a0
4 6
3/2
3/2
2 p R2,1 (r ) Y1,1 ( , )
Z
1
1/2 a0
4 6
/4
3
e
sin
3 2
i
e /4 8 sin e

Real wavefunctions could be defined by linear combinations of complex

wavefunctions such that now the orientation of the maximum probability
density could be identified.
5
zr
2
1 z
2a
2 p1 2 p1
e 0 r sin cos 2 p x
16 a0
x= r sin cos
1 nodal surface (yz plane)
2 p 2 p
1
5
2
zr
1 z 2 a0
1
e r sin sin 2 py
i
16 a0
1 nodal surface (xz plane)
Y = r sin sin
5
2p orbitals boundary surfaces
2p
No. of Radial Node: n-l-1
No. of angular Node: l
Total no. of nodes: (n-1)
and
2p
These non-imaginary wavefunctions

are not the eigenfunctions of Lz
(ml cannot be determined).
but are still the eigenfunctions of
energy and total angular momentum.
6
3dz2 orbitals boundary surfaces
3, 2,0 3d
z2
1
2
zr
1 6 Z 3 z 2 r 2 3 a0
2
3
e
3
cos
1
2
486 a0 a0
n = 3, l = 2, ml = 0
No. of Angular nodes l = 2
1 6Z
3
486 a0
1 6Z
3
486 a0
1
2
z
2 e
a0
1
2
z
2 e
a0
2
zr
3 a0
zr
3 a0
3r
cos2 r 2
z = r cos
3z
r2
Other 3d orbitals (ml 0)

1 z3
A 3
81 a0
1 z
B 3
81 a0
3
1
2
1
2
zr
z 2 r 2 3a0
2 e . sin cos .ei
a0
z r
2
a0
2 2
zr
3 a0
. sin cos .e i
n = 3, l = 2, ml = =1 or -1
No. of Angular nodes l = 2
These are not real wavefunctions.

In which direction, the maximum probability density will be oriented ?
8
3dxz & 3dyz orbitals boundary surfaces

3d 3d
1
3d 3d
1
7
2
7
2
3d xz
3 d 3 d
1
2 z
e
81 a0
3d yz
zr
3 a0
.r sin cos .r cos

No. of angular
Nodes: l = 2
x
3 d 3 d
zr
1 z 3 a0 2
e r sin 2 cos
81 a0
7
2
zr
7
2
zr
3 a0
1 z 3 a0 2
e r sin 2 sin
81 a0
2 z
e
81 a0
.r sin sin .r cos

y
9
z
3dx2-y2 & 3dxy orbitals boundary surfaces
81 2
3d 3d
2
81 2
3d
7
2
7
2
x2 y 2
3d 3d
2
zr
z 3 a0 2 2
e r sin cos 2
a0 7
zr
z 2 3 a0 2 2
e r sin cos2 sin 2
a0
zr
2
1 z 3 a0
2
e
r
sin
cos
(
r
sin
sin

81
2
a0
7
2
zr
1 z 3a0 2 2
e r sin sin 2
81 2 a0
7
2
zr
1 z 3 a0 2 2
e r sin .2 sin cos

81 2 a0
3d
7
2
xy
zr
1 z 3 a0
e r sin cos )(r sin sin

81 2 a0
10
General form of 4px orbital for H atom ?

For a 4px orbital:
n = 4, l = 1
ml = cannot defined with accuracy.

No of angular nodes = 1 = l
(i)The power of r (or ) = l = 1

(ii) Polynomial in r (or ) should have maximum power = n-l-1 = 2
(iii) Px will be obtained by linear combination of ml= =1 and -1
and it will have a form, x= r sin cos

(iv) Exponential term in power zr/na0
4 p
1
4 p1
4 px N .e
11
zr
4 a0
r (ar 2 br c) sin cos

Most Probable distance

Most Probable Radius: could be obtained by putting
dP(r)/dr = 0
Position of principal (largest) maximum depends on n and l
For fixed l it increases to larger r values
12
Most Probable distance

For fixed n it moves to shorter r values as l
increases
(r3d)max < (r3p)max< (r3s)max
13
Electron Spin
Spin of an electron is an Intrinsic angular momentum,
which cannot be changed or eliminated.
Electron spin is defined by a spin quantum number, s

with its fixed values of for all electrons.
The spin can be clockwise or anticlockwise, these states
are distinguished by spin magnetic quantum number, ms,
where ms can take the values = 1/2 or -1/2.
Existence of electron spin was demonstrated by Stern and

Gerlach Experiment.
Self Study-Text Book, Pg 325
14
Spin states of electron
The state of the electron in the hydrogenic atom is therefore

fully specified by the four quantum numbers n, l, ml, and ms.
15
Spin
All fundamental particles have characteristic spin values.
Protons and Neutrons are also spin particles like
electrons.
Photons are spin 1 particles.
All particles may be classified as BOSONS (spin
quantum number is zero or a positive integer, ie., s =
0,1,2,)
FERMIONS (spin quantum number is a positive halfinteger, ie., s = 1/2, 3/2,.. )
16
Spectral Transitions
In the one electron atom, spectral line occurs when electron
makes a transition between shells with principal quantum
numbers ni and nf. However, not all transitions between all
available orbitals are possible.
For example,
2p to 1s, and 3p to 1s are allowed transitions,

2s to 1s or 3d to 1s are forbidden transitions.
A statement about which spectroscopic transitions are allowed
is called a selection rule
17
Selection rule one electron atom

For the one electron atom, the selection rule is just the
statement of the conservation of angular momentum.
During a transition, angular momentum must be conserved.
When a photon is released (or absorbed) in a transition, the
angular momentum of the electron must change in order to
compensate for the angular momentum carried away by
photon.
Selection rule:
l = 1
ml = 0, 1
The principal quantum number can change by any amount consistent
with the l for the transition because n is not directly related
to angular momentum.
18
Grotrian Diagram
l = 1
ml = 0, 1
19
Many-Electron Atoms
Schodinger Equation for a many-electron atom is highly complex
because all electrons are interacting with each other.
Helium Atom (Two electrons): electrons 1 and 2:
Mathematical expression for orbitals and energies cannot be given.
Orbital approximation: The wavefunction of non-interacting

particles is the product of avefunction of each particle.
(1,2,) = 1(1)2(2)..
The Orbital approximation allows us to express the electronic
structure of an atom in the form of configuration: A Statement of
orbital representation that are occupied. (but not necessarily in the
ground state)
H (Electronic Configuration): 1s1
20
Orbital approximation He atom

Each orbital may be thought of as being hydrogen-like with an
effective nuclear charge.
The 1st electron of helium occupies the 1s hydrogenic orbital and
since Z for He is 2 so this 1s orbital can be assumed to be more
compact that it can accommodate a second electron leading to
He (Electronic Configuration):1s2
If one disregards the inter-electronic repulsion, the ground state
wavefunction of He may be written as
(1,2) = (8/a03)1/2 e-2r1/a0 (8/a03)1/2 e-2r2/a0
21
BITS Pilani
Pilani Campus

Lecture 9
Summary (Lecture 8)
-Interpretation of total wave function of orbital
-Recognizition of orbitals from wavefunction
Electron spin
Selection Rule for Hydrogenic atoms
Many electron atom
-Orbital approximation
Orbital Approximation
We construct a helium wave function as the product of
hydrogenic orbitals with Z = 2.
(1,2) = (1)(2)
If one disregards the inter-electronic repulsion, the ground state
wavefunction of He may be written as
(1,2) = (8/a03)1/2 e-2r1/a0 (8/a03)1/2 e-2r2/a0
Two Issues in this equation
Issue #1: an electron is fermion and fermions wave function must

be antisymmetric with respect to interchange:
Fermions
(2,1) = - (1,2)
(Pauli principle)
Issue #2: each electron must be either spin or

3
Antisymmetric wavefunction
Two electrons in same orbital (spatial wavefunction) :
(1,2) = (1) (2){spin part}
Pauli principle: (1,2) = - (2,1) (MUST FOLLOW!)
How spin part could be (for two electrons in an orbital)?

or
or
Antisymmetric wavefunction
What will be the form of the wavefunction?
(1,2) = (1)(2)
(1,2) = (1)(2)
(1,2) = (1)(2) { +}
(1,2) = (1)(2) { - }
It should be antisymmetric with respect to
exchange of the electrons' coordinates and
should be indistinguishable.
(1,2) = (1)(2) { -}
5
Pauli exclusion principle

What about Li? (Can all 3 electrons occupy 1s
orbital ?)
No more than two electrons may occupy a given orbital,
and if two electrons do occupy one orbital, then their spins
must be paired.
The two electrons with paired spins ( have zero net
spin angular momentum.
This principle forms the basis of the electronic structure of
atoms, chemical periodicity, and molecular structure.
The third electron in Li must enter the n = 2 shell, but
the 2s or the 2p?
6
Shielding
In a hydrogenic atom (with only one electron), s, p, d orbitals
in the same shell are degenerate.
However, for more than one electrons, this will no longer be

true.
In a many electron atom, each electron is shielded from the
nucleus by the others, and to a first approximation, each electron
may be thought of as experiencing an effective nuclear charge,
making the outer orbitals energies higher.
The effective nuclear charge experienced by an electron will be
determined by its probability density distribution, and this in turn
by its wavefunction.
7
Shielding & Penetration

The s functions have greater probability density near the
nucleus than p or d in the same shell and experience less
shielding.
Order of occupation
The greater penetration of an s electron compared to a p
electron of the same shell implies that it experiences a
greater effective nuclear charge.
In turn, the effective nuclear charge experienced by the p
electron will be greater than that for a d electron in the
same shell.
In general therefore, in the same shell of a many-electron
atom, the order of energies of the orbitals is s < p < d < f.
The ground electronic configuration of Li is therefore
1s22s1, or [He]2s1
9
Building up Principle
The extension of procedure used for H, He and Li to other
atoms.
Rule 1. Order of occupation of atomic orbitals follows:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 5d 4f 6p
(Aufbau principle)
Rule 2. Each orbital may accommodate up to two electrons
(Pauli principle)
Rule 3. Electrons occupy different orbitals of a given subshell
before doubly occupying any one of them.
N (Z = 7): 1s22s22px12py12pz1
; N (Z = 8): 1s22s22px22py12pz1
Rule 4. In its ground state, atom adopts configuration with

greatest number of unpaired electrons (Hunds rule)
10
Hunds rule, periodicity

Eg., C 1s22s22px12py1
N 1s22s22px12py12pz1
Origin of Hunds rule: Complicated explanation

Quantum mechanical property of Spin Correlation
Electrons in different orbitals with parallel spins have a
quantum mechanical tendency to stay apart.
This allows slight shrinkage of atom, leading to greater
attraction between nucleus and electron.
Periodicity: Neon with ten electrons has the configuration
[He]2s22p6, which completes the L shell. Na has
configuration [Ne]3s1, with properties like Li
11
Periodic Table
Ar - [Ne]3s23p6 effectively like closed shell.
Next the 4s orbitals are filled (penetration).
K [Ar]4s1 (like Na) and Ca [Ar]4s2 (like Mg).

The 3d orbitals are filled next from Sc to Zn the first
transition series, d-block elements
Sc [Ar]3d14s2, Zn [Ar]3d104s2
(Y to Cd, and La to Hg are second & third series).
Beyond this from Ga to Kr, the 4p orbitals are filled (the
first long period)
In periods 6 and 7 also have f-block elements
12
Configuration of cations & Anions

The configuration of cations of elements in the s, p, and d
blocks o periodic table are derived by removing electrons from
the ground state configuration of neutral atom in a specific
order.
Cu (GS): 1s2 2s2 2p6 3s2 3p6 4s1 3d10
Cu2+ : 1s2 2s2 2p6 3s2 3p6 3d9 OR [Ar] 3d9

Cu1+ : 1s2 2s2 2p6 3s2 3p6 4s1 3d9
The configuration of anions are derived by continuing the
building up procedure and adding electrons to the neutral atom
until the configuration of the next boble gas has been reached.
S (GS): 1s2 2s2 2p6 3s2 3p4

S2- : 1s2 2s2 2p6 3s2 3p6 OR [Ne] 3s2 3p6
13
Periodic Properties
Atomic Radius
Ionization Energy - Minimum energy for process
E(g) E+(g) + e-
I1 = E(E+) E(E)
Electron affinity is the difference in energy between

neutral atom and anion.
E(g) + e E(g)
Eea = E(E) E(E)

Self Study-Text Book, Pg 332-335
14
The spectra of complex atoms:

The spectra of many-electron atoms can be complicated.
A great deal of information could still be interpreted about the
interaction between electrons.
We consider some notations to specify the states of an multielectron atom.
The energy level of an atom is called a term and the notation

used to specify the term is called a TERM SYMBOL
Electronic configuration (C): 1s2, 2s2, 2p2

How many electronic states of a Carbon atom are possible
corresponding to its electronic configuration ?
15
TERM SYMBOLS
This scheme to arrive at term symbols is called Russell
Saunders coupling.
It is based on the fact that orbital and spin angular
momentum of an electron couples (spin-orbit coupling) to
give resultant momentums and all these resultant
momentums of different electrons further couples to give an
overall total angular momentum.
This total angular momentum can determine the energy of a
system and the changes in energy that are observed during a
transition.
The calculations only focus on valence electrons.
The core or inner electrons do not contribute to the overall
angular momentum of the atom.
16
Orbital and spin angular momenta

Electron has spin angular momentum
Moving charges generate magnetic fields

Magnetic moment from spin
Electron has orbital angular momentum (l>0)

Magnetic field generated from orbital momentum
Magnetic moment from orbital angular momentum
17
Spin-orbit interaction, j
l
Magnetic moments are parallel

(angular momenta are parallel)
HIGH ENERGY
High value of j
l
Magnetic moments are antiparallel
(angular momenta are antiparallel)
LOW ENERGY
Low value of j
Depending upon the relative orientation of spin- and orbitalangular momenta, the total angular momentum can be
calculated in terms of a quantum number, j
18
Spin-orbit interaction of a single electron

Relative orientation of the spin and orbital angular momenta.
Use of vector representation to note coupling of spin and
orbital angular momenta
Two angular momenta

adding
s
j=l+s
Two angular momenta

opposing
Total angular
momenta could be
represented
j = |l s|
j =| l - s |
For an s-electron: l = 0, s = 1/2; j = 1/2 only

For a p-electron: l = 1, s = 1/2; j = 3/2 or 1/2
For a d-electron: l = 2, s = 1/2; j = 5/2 or 3/2
19
For two electron system:

Total orbital & spin angular momentum
Total orbital angular momentum could be represented as
L = l1 + l2, l1 + l2 1, l1 + l2 2,.., l1 l2
Two orbital ang.
momenta are in
same direction
Two orbital ang.

momenta are in
opposite direction
Clebsch-Gordan Series
Total spin angular momentum could represented as
S = s1 + s2, s1 + s2 1, s1 + s2 2,.., s1 s2
20
Total angular momentum

We have seen that j gives relative orientation of spin
and orbital angular momentum of single electron
J = L+S, L+S 1, ., |L-S|

Russell-Saunders coupling
Total angular momentum quantum number J

does same thing for multi-electron system.
21
Information from Term Symbol

Electronic states of an atom corresponding to its electronic
configuration
Information about S and
multiplicity
Information about L,
Total orbital angular
momentum quantum
number
2S+1
L
Code for conversion
to letter:
J
Information about J, Total
angular momentum (spin and
orbital) quantum number
L = 0(S), 1(P), 2(D),

3(F), 4(G), 5(H), 6(I),
22
State for a s1 System

Configuration: 1s1
l1 = 0 = L
s1 = 1/2 = S
j = J = 0+1/2, ., |0-1/2|
J = 1/2
The state for this configuration is represented by:
2S+1
L
J
S
1/2
For each j, there could be two different orientations of

j possible given by mj = amd mj = -
23
States for a 2p1 System

Completely filled subshells do not contribute
to the total angular momentum of an atom
EC: 1s22s2 2p1
l1 = 1 = L
s1 = 1/2 = S
J = 1+1/2, ., |1-1/2|
J = 3/2, 1/2
The state for this configuration is represented by:
2S+1
L
J
(doublet)
2
and
P
3/2
P
1/2
For each j, there could be (2j+1) different orientations

of j possible given by mj j to +j (in integral steps)
24
BITS Pilani
Pilani Campus

Lecture 10
Summary (Lecture 9)
Helium Atom:
-Orbital Approximation
Building up Principle
-Aufbau principle
-Pauli principle
-Hunds rule
-Shielding & Penetration of orbitals
Electronic configuration of atoms & ions

TERM SYMBOLS
2
TERM SYMBOLS
For a multi-electron atoms, the spectrum or transitions
between different levels could only be explained if we define a
new system of Term/Energy levels/states that takes into account
the interaction between electrons (in terms of considering the
coupling between orbital and spin angular momentum of
electrons).
In this new system, the energy level of an atom is called a

term, and the notation used to specify the term is a TERM
SYMBOL.
This scheme to arrive at term symbols is called Russell
Saunders coupling.
3
Total orbital & spin angular momentum

Total orbital angular momentum could be represented as
L = l1 + l2, l1 + l2 1, l1 + l2 2,.., l1 l2
Clebsch-Gordan Series
Total spin angular momentum could represented as
S = s1 + s2, s1 + s2 1, s1 + s2 2,.., s1 s2
Russell-Saunders coupling
J = L+S, L+S 1, ., |L-S|

Total angular momentum quantum number,
J for multi-electron system.
4
Information from Term Symbol

Electronic states of an atom corresponding to its electronic
configuration
Term
Information about S and
multiplicity
Information about L,
Total orbital angular
momentum quantum
number
2S+1
L
Code for conversion
to letter:
Term Symbol
Energy Level
Information about J, Total

angular momentum (spin and
orbital) quantum number
L = 0(S), 1(P), 2(D),

3(F), 4(G), 5(H), 6(I),
5
State for a s1 & p1 System System

Configuration: 1s1
Configuration: 1s22s2 2p1
l1 = 0 = L
s1 = 1/2 = S
j = J = 0+1/2, , |0-1/2|
J = 1/2
2S+1
l1 = 1 = L
s1 = 1/2 = S
J = 1+1/2, ., |1-1/2|
J = 3/2, 1/2
S
J
3/2
1/2
1/2
For a given value of J, total number of degenerate states = 2J+1,

distinguished by the quantum no. MJ. J to +J (in integral steps)
6
Two p electrons (in different shells 2p13p1)

Excited state configuration of C is [He]2s22p13p1
l1 =1, l2=1
L = l1 + l2, l1 + l2 1, l1 + l2 2,.., l1 l2.
L = (1+1=2), (1+1-1=1),1-1=0.
L = 2(D), 1 (P), 0 (S) DIFFERENT POSSIBLE RELATIVE
ORIENTATIONS OF THE TWO ORBITAL

ANGULAR MOMENTA
S = s1 + s2, s1 + s2 1, s1 + s2 2,.., s1 s2.

s1 = & s2 =
Multiplicity: 2S + 1
S = 1,0
S = 0 (Singlet); S = 1 (Triplet)
7

L = 2(D), 1 (P), 0 (S)
2S+1
S = 1,0
Triplet terms: 3D, 3P, 3S

Singlet terms: 1D, 1P, 1S
J
J = L+S, L+S 1, ., |L-S|
For each term J needs to calculated separately:

A term with different J values represent different level.
For a given term, number

of states (2L + 1)(2S + 1)
For a given conf., number

of states, b!/(b-a)!a!
b: total possible positions:
a : total no of electrons
8

3D
term: L = 2 and S = 1,
So J = 3,2,1. Levels are 3D3
3D
2
3D
1
P term, L = 1 and S = 1,
So, J = 2,1,0. Levels are : 3P2
3P
1
3P
0
3S, : L = 0 and S = 1,
J = 1.
Level is 3S1
1D term: Level is : 1D
2
1P term: Level is: 1P
1
1S term: Level is: 1S
0
7 Degenerate states
15 Deg. states
5 Degenerate states
(2L + 1)(2S + 1)
(2x2+1)(2x1+1)=15
3 Degenerate states
5 Degenerate states
9 Deg. states
3 Degenerate states
(2L + 1)(2S + 1)
(2x1+1)(2x1+1)=9
1 Degenerate states
3 Degenerate states
5 Degenerate states
3 Deg. States
(2x0+1)(2x1+1)=3
3 Degenerate states
5 Deg. States
3 Deg. States
1 Degenerate states
1 Deg. States

For a given term, number
of states (2L + 1)(2S + 1)
For a given conf., number

of states, b!/(b-a)!a!
b: total possible positions:
a : total no of electron
3D
term, 15
3P term: 9
3S term: 3
1D term: 5
1P term: 3
1S term: 1
Total no. of states: 36
3D, 3P, 3S, 1D, 1P, 1S
For a 2p13p1
number of states =
6!/(6-1!)1! x 6!/(6-1!)1!
number of states = 36
:All levels exist for this configuration

10
Determining the ground state term:

Hunds rule
I The term with the greatest multiplicity lies lowest in energy.
The ground state therefore possesses the most unpaired spins
because this gives the minimum electrostatic repulsion.
So one of the terms 3D, 3P, 3S arising from [He]2s22p13p1
configuration lies lowest.
II The term with the greatest orbital angular momentum lies lowest
in energy.
So 3D term mentioned above will lie lowest of all the terms.
IIIa The level with lowest J lies lowest in energy if the subshell is
less than half filled.
IIIb The level with highest J lies lowest in energy if the subshell is
half or more than half filled.
Rule III is not applicable for excited configurations.
11
G. STATE term symbol determination

Without determining all the levels/states, one can directly
determine the ground state term symbol for any configuration.
Ground State Term should correspond to a term with the

greatest multiplicity (lowest energy) or a state with most
unpaired spins.
For each configuration: We could determine the Ground
State Term by first choosing the max. S (considering ms)
and determine the corresponding max. L possible (by
considering the ml for the orbitals).
ml
ml
+2 +1 0 -1 -2
+1
0
-1
ms
ms
12
G. STATE term symbol Determination

Both electrons are
2p1 3p1 Configuration:
For max. S; s1 = & s2 = in parallel spin
2 (D) = Max. L possible

2p1
ML = (1 +1)
3p1
ml
+1
Max. S = 1
=2S+1 = 3
ml
+1
-1
-1
ms
ms
Ground State Term: 3D

13

Both electrons are
2p2 Configuration:
For max. S; s1 = & s2 = in parallel spin
Max. S = 1
=2S+1 = 3
ML= (1 +0)
1 (P) = Max. L possible
ml
2p2
+1
0
-1
ms
Ground State Term: 3P
L = 1 and S = 1,
3P 3P 3P
2,
1,
0
So J = 2,1,0
G.S term of p4 Configuration will be same as p2 confi.,
assuming the filling of holes instead of electrons
14

d3 /d7Configuration:
For max. S s1 =
s2 =
s3 =
three electrons should be Max. S = 3/2

in parallel spin
=2S+1 = 4
3 (F) = Max. L possible
ML= 2 + 1 + 0
ml
+2 +1 0 -1 +2
ms
4F
9/2
4F
7/2
4F
5/2
4F
3/2
Ground State Term: 4F

For a 4F term, J can be calculated
L = 3 and S = 3/2,
So J = 9/2,7/2,5/2,3/2.
Ground State Energy Level (d7 conf.)
Ground State Energy Level (d3 conf.)
15
BITS Pilani
Pilani Campus

Lecture 11
Summary (Lecture 10)

TERM SYMBOLS
How to determine term symbols for a configuration.
s1, p1, (p1 p1)
Arranging the terms/levels in increasing order of energy
(Hunds Rule)
Determing the No. of states/microstates for a
configuration.
Directly determining the Ground State term/levels of a

configuration.
2

Without enumerating all the states, what is the term of lowest
energy that arises from the ground electronic configuration of N?
N; p3 :
Max. S = 3/2
goes only with ML = 0 (S = 3/2 with only L = 0 (S)
Ground Term:
4S
4S
d1Configuration:
2D
3/2
d9 Configuration: 2D5/2
3/2
d2 Configuration: 3F2
d8 Configuration: 3F4
p1 Configuration: 2P
p5 Configuration: 2P
1/2
3
3/2
Two p electrons in same shell 2p2

The two electrons in a p sub-shell are in-distinguishable.
For a p2 system the term determination will be same as
2p13p1 system but All terms are not possible for a p2
configuration. 3 3 3 1 1 1
D, P, S, D, P, S
Pauli principle places restrictions

3P
(9 states), 1D (5 states), 1S (1 states)

3P (1 state), 3P (3 states) 3P (5 states) ,1D (5 states) 1S (1 states)
0
1
2
15 states for p2
lowest energy
Discussion in Tutorial Class

4
Selection Rules
For spectroscopic transitions in many-electron
atoms:
L = 0, 1
S = 0
J = 0, 1 (but J =0 J = 0 is forbidden)
For heavier atoms, first coupling of l and s for individual
electrons occur to get j values for each electron which then
couple with other j to get final J
j-j coupling method. (Not in syllabus)
5
Term Symbols: Explains the Spectra

Question The Sodium D emission line spectra is actually a
doublet, i.e., two very closely spaced lines. Explain.
Answer: This means transition from excited level of Na

(3p) to Ground level of Sodium (3s)
Due to spin-orbit coupling the 3p (l = 1, s = ) configuration
actually splits into two levels, corresponding to total angular
momentum quantum number j = 3/2 (l + s), and (l s): 2P3/2 &
2P
1/2
3s (l = 0, s = ) configuration correspondsto total angular

momentum quantum number j = 1/2 (l + s): 2S1/2
Two lines are due to transition: 2P3/2
2P
1/2
6
2S
2S
1/2
L = 1, S = 0, J = 1
1/2
L = 1, S = 0, J = 0
Chemical Bonding
Electronic Structure of Molecules

Electrons in molecules are described approximately with
orbitals just like electrons in atoms are described by orbitals
How does quantum mechanics treat Molecular Orbitals?

Rather than being localized on individual atoms an electron
in a molecules has wavefunctions that extends over the entire
molecule.
There are two approaches towards the calculation of molecular
structure (describing molecular orbitals): [to construct the
wavefunction for electrons in molecules]
1. Valence Bond Theory
2. Linear Combination of Atomic Orbitals Molecular Orbitals
(LCAO-MO)
8
The Schrdinger Equation for molecules

All properties of a molecule (= M nuclei + n electrons) can be
evaluated if we find the wavefunction (x1, x2,..., xn) by solving
the Schrdinger equation (SE): H =E.
H= Ttot + Vtot= (TN + Te )+ (VeN + Vee + VNN)
The total kinetic operator of the molecule is composed of a part for
the nuclei TN and for the electrons Te. The total potential energy
operator is the sum of the electron/electron (Vee), electron/nucleus
(VeN) and nucleus/nucleus (VNN) interactions.
Solving with the best approximation the Schrdinger equation is
the challenge of quantum chemistry
9
The Born-Oppenheimer approximation

The electrons are much lighter than the nuclei their motion is
much faster than the vibrational and rotational motions of the
nuclei within the molecule.
A good approximation is to neglect the coupling terms between
the motion of the electrons and the nuclei: this is the
Born-Oppenheimer approximation
The Schrdinger equation can then be divided into two
equations:
1) One describes the motion of the nuclei.
2) The other one describes the motion of the electrons around the
nuclei whose positions are fixed. This electronic part of the
Schrdinger equation is the electronic Schrdinger equation:
10
The electronic Schrdinger equation
elect
elect
Te VeN Vee (R, r ) = Eelect (R, r )
The nuclear coordinate R appears as a parameter in the

expression of the electronic wave function.
An electronic wave function elect(R,r) and an energy Eelect are
associated to each structure of the molecule (set of nuclei
coordinates R).
For each variation of bond length in the molecule (each new R),
the electronic SE can be solved and the energy that the molecule
would have in this structure can be estimated: the molecular
potential energy curve is obtained.
The molecule is the most stable (minimum of energy) for one
specific position of the nuclei: the equilibrium position Re.
11
The Electronic Schrdinger Equation:

Energy Eigen Value
elect
elect
Te VeN Vee (R, r ) = Eelect (R, r )

12
Valence-bond theory
A bond is regarded as forming when an electron in an atomic
orbital on one atom pairs with that of an electron in an atomic
orbital on another atom.
One can consider the molecular wavefunction in terms of
product of atomic orbitals.
Overlapping of the orbitals that gives rise to a bond is
accompanied by spin pairing of the electrons.
Hydrogen molecule as an example
At infinite interatomic separation, each hydrogen atom (HA and
HB) has its own independent wavefunctions.
HA = 1sHA(1)
HB = 1sHB(2)
When the two atoms come together to make hydrogen molecule:
[there is an equal possibility that electron 1 can be found in B and
electron 2 in atom A.
13
Valence-bond theory-H2
The wavefunction of the complete system
is
= HA HB = 1sHA(1) 1sHB(2)
Thus, the wavefunction could also be

possibly written as:
= HA HB = 1sHA(2) 1sHB(1)
Whenever two outcomes are equally likely, the quantum
mechanics tells to add together or superimpose such
wavefunctions. Thus, the (un-normalized) wavefunction
could written as:
H-H (1,2) = HA (1)HB (2)+ HA (2)HB (1)
14
The total electronic wavefunction (1,2) of H2 must be
antisymmetric and takes into account the spin part and Pauli
principle.
(1,2)= +(1,2) S(1,2)= +(1,2) {(1)(2) - (1)(2)}
The spatial orbital +(1,2) gives an energy for the 2-H system
that is lower than the energy of 2 Hydrogen atoms far from each
other.
This wavefunction has cylindrical symmetry about the internuclear axis, and is said to represent a -bond.
15
We can calculate the energy of this molecule by substituting the
valence bond wavefunction into the schrodinger equation and carrying
out necessary mathematical manipulations:
As two atoms approach each other there is accumulation of

electron density between two nuclei, which is at the expense of
removing electron density from close to the nuclei.
Note the pile-up in the region
between the nuclei.
16
Valence-bond theory: N2
Similar description may be used for diatomics built from atoms
that contribute more than one electron to bonding:
N2 molecule.
Each atom has three 2p electrons available
for bonding.
N: 1s2 2s2 2pX1 2py1 2pZ1
With the inter-nuclear axis named z-axis,
the overlap of the 2pz orbitals and the
pairing of those electrons leads to a -bond
being formed.
17
Valence-bond theory: N2
The two 2px orbitals overlap
in side-wise fashion, and
their electrons pair to form a
-bond.
Likewise, the merging

of the two 2py orbitals
leads to another -bond
18
Valence-bond theory: Polyatomic

molecules
H2O: The two unpaired electrons in O atom can each pair
with an electron in an H 1s orbital, leading to two bonds.
The molecule is predicted to be bent, at an angle of 90.
whereas the actual bond angle is 104.5.
O: 1s2 2s2 2px2 2py1 2pz1
H1s1
19
H1s1
Valence-bond theory: Deficiencies

Poor estimations on the bond angles of the molecule .
e.g H2O & NH3
Inability to account for the number of bonds that atoms can form.
Eg. Tetravalence of carbon. C: 1s2 2s2 2pX1 2py1
Modifications to solve these deficiencies
1. Assumption: Atoms are in their lowest energy configurations.

II. Allow a valence electron to promote from a full atomic
orbital to an empty atomic orbital, which results in two
unpaired electrons capable of participating in bond formation.
20
Hybrid Orbitals
Consider first the example of methane, with four equivalent C-H
bonds.
Ground state C: 1s22s22px12py1
Promote one electron to get 1s22s12px12py12pz1
This excited atom is capable of forming three -bonds of onetype and one -bond of another type.
However, experimentally: All four C-H bonds are exactly

equivalent.
Quantum mechanics permits the same electron distribution to be
described in different ways. Electronic distribution arising from
four electrons in four different mixtures of these orbitals.
Mixtures of atomic orbitals of same atom: Hybrid orbitals.
21
Hybridization-sp3
An orthonormal set of hybrid orbitals is created by applying a
transformation on the orthonormal hydrogenic orbitals by mixing one
s and three p orbitals.
Four equivalent sp3

hybrid orbitals:
h1= N(s + px + py + pz)

h2= N(s - px + py - pz)
h3= N(s - px - py + pz)
h4= N(s + px - py - pz)
Signs before
coefficients represent
orientation or direction
of hybrid orbitals.
h1 : + x, + y, + z
h2 : - x, - y, + z
h3 : - x, + y, - z
h4 : + x, - y, - z
Four hybrid orbitals are pointed towards the corner of tetrahedron.

22
Hybridization-sp3
1
N
4
h1= N(s + px + py + pz)

h3= N(s - px - py + pz)
h2= N(s - px + py - pz)

h4= N(s + px - py - pz)
An orbital is equally contributed to four hybrid orbitals. Thus its

contribution in any hybrid orbital should be 1/4.
Contribution in a hybrid orbital = (Coefficient of an orbital)2
In any Hybrid orbital:
The squares of the coefficients give the
relative proportions of the different orbitals
2
1
1
s : p 1.
: 3.
4
4
sp3
Electron in each of these sp3 hybrid orbitals pairs up with electron

in H 1s orbital forming -bonds, all four of which are identical.
23
BITS Pilani
Pilani Campus
CHEM F111 :
GeneralChemistry
Lecture 12
1
Summary (Lecture 11)

TERM SYMBOLS
SELECTION RULES
CHEMICAL BONDING
VALENCE BOND THEORY
HYBRIDIZATION
Hybridization-sp3
An orthonormal set of hybrid orbitals is created by applying a
transformation on the orthonormal hydrogenic orbitals by mixing one
s and three p orbitals.
Four equivalent sp3

hybrid orbitals:
h1= N(s + px + py + pz)

h2= N(s - px + py - pz)
h3= N(s - px - py + pz)
h4= N(s + px - py - pz)
Signs before
coefficients represent
orientation or direction
of hybrid orbitals.
h1 : + x, + y, + z
h2 : - x, - y, + z
h3 : - x, + y, - z
h4 : + x, - y, - z
Four hybrid orbitals are pointed towards the corner of tetrahedron.

3
Hybridization-sp3
1
N
4
h1= N(s + px + py + pz)

h3= N(s - px - py + pz)
h2= N(s - px + py - pz)

h4= N(s + px - py - pz)
An orbital is equally contributed to four hybrid orbitals. Thus its

contribution in any hybrid orbital should be 1/4.
Contribution in a hybrid orbital = (Coefficient of an orbital)2
In any Hybrid orbital:
The squares of the coefficients give the
relative proportions of the different orbitals
2
1
1
s : p 1.
: 3.
4
4
sp3
Electron in each of these sp3 hybrid orbitals pairs up with electron

in H 1s orbital forming -bonds, all four of which are identical.
4
Hybridization-sp2
The sp2 hybrid atomic orbitals lie in a plane and points towards
the corners of an equilateral triangle .
Three equivalent sp2

hybrid orbitals:
+21/2
1
N
3
1 2
s: p
:
3 3
2
h1= N(s
py)
h2= N(s + (3/2)1/2 px - (1/2)1/2 py )
h3= N(s - (3/2)1/2 px - (1/2)1/2 py )
1 3 1
s: p
3 2 3 2 3
2
sp2
Hybridization-Ethene-sp2
(a) Sp2 Hybrid orbitals form -bonds
with H atoms or the other C atom.
(b) The remaining unhybridized 2p orbitals
(2pz) on the C atoms are not involved in
the hybridization, and its axis is
perpendicular to the plane of the triangle.
And they form -bond.
H
H
H
6
Hybridization-Ethyne-sp
The sp hybrid atomic orbitals lie along an axis.
Two equivalent sp
hybrid orbitals:
h1= N(s + pz )
h2= N(s pz)
1
2
1 1
s: p
:
2 2
In ethyne, HCCH: Formation of 2

bonds (with C and H) using the 2
hybrid atomic orbitals h1 and h2. The
remaining 2px and 2py can form two
bonds between the two carbon
atoms.
7
sp
x
y
Hybridization
There could be more
possibilities than these
pure schemes.
For example: If in a sp-hybrid orbital, if we start increasing the pcharacter then new hybrid orbitals with intermediate
proportions of atomic orbitals, may result.
8
Resonance
(Ionic-covalent resonance: Resonance hybrid)
What about HF?
c(1,2) = {a(1)b(2) + b(1)a(2)} { }
with a and b being the 1s of H and the 2pz of F
But HF is polar. So expect to have ionic character also.

i(1,2) = b(1)b(2) { } also to be reasonable.
To account for both the characters:
Write = c + i (trial wave function).

2 represents relative proportion of the ionic
contribution.
Expressing a wavefunction as the superposition of wavefunctions
corresponding to a variety of structures with the nuclei in the
same location is called Resonance
9
Molecular orbital (MO) theory

The individual orbitals of separate atoms combine to
make orbitals that span the entire molecule.
We can construct the MO by taking linear combinations
of the occupied atomic orbitals.
Hydrogen molecule-ion: H-H+
The electron may be found in an atomic orbital (AO) belonging
to atom A (i.e.; 1s of H) and also in an atomic orbital belonging to
B (i.e.; 1s of H+)
The total wavefunction should be a superposition of the 2

AO and it is called Molecular orbital LCAO-MO.
= N(A B)
N is the normalization constant.
10
Molecular orbital (MO) of H2+

Hydrogen molecule-ion: H-H+
= N(A B)
Antibonding
Bonding
G.S. Conf. of H2+: 11

Note increased electron density between nuclei in bonding case,
and the node midway between nuclei in antibonding case.
11
Overlap Integral, S
The accumulation of probability density in the internuclear
region is measure by the Overlap integral, S
S = 1 Perfect overlap
S = 0 No overlap
S : between 0 & 1 intermediate overlap between no &
perfect overlap possible. overlap
Greater the overlap integral, stronger is the bonding

effect of electrons in the molecular orbital they form.
12
Overlap Integral, S for two H1s orbitals

Ovelap integral, S is calculated by dividing the space up
into a large number of regions and multiplying together
the values of A and B and then adding together the
resulting products of all regions (integrating).
13
Overlap Integral, S
+= N(A + B):
2
2
2
A
B d 2 A B d 1
N 2 (1 1 2 S ) 1
1
N
1/ 2
2(1 S )
S AB d
is the overlap integral related to the overlap of the

2 AO
14

The hydrogen molecule-ion: H-H+
Bonding orbitals
+= {2(1+S)}-1/2(A + B), with A=1s, B=1s of H
Probability density: 2+= {2(1+S)}-1(A2 + B2 + 2AB)
A2 = probability density to find the e- in the atomic
orbital A
B2 = probability density to find the e- in the atomic
orbital B
2AB = the overlap density represents an
enhancement of the probability density to find the ein the internuclear region: the electron accumulates
in regions where AOs overlap and interfere
constructively; which creates a bonding orbital 1
with one electron.
15
2+

The hydrogen molecule-ion: H-H+
Antibonding orbitals
2-
-= {2(1-S)}-1/2(A - B)
Probability density: 2-= {2(1-S)}-1(A2 + B2 2AB)
-2AB = reduction of the probability density to
find the e- in the internuclear region: there is a
destructive interference where the two AO
overlap, which creates an antibonding orbital
*.
Nodal plane between the 2 nuclei
16

Hydrogen molecule-ion: H-H
G.S. Conf. of H2: 12

17
He2 ground state (1)2 (1*)2
He2 is not stable and does not exist.

Energy drop of the pair of electrons in the 1s orbital is negated
because the other pair in the *1s rises in energy by an equal amount.
There is thus no net stabilization, and so the He2 molecule does not
exist. It exist as a monoatomic gas.
18
Molecular Orbitals using p Atomic Orbitals

and from the pz orbitals
19
orbitals
The 2px and 2py orbitals lead to a pair of and

a pair of * orbtals
20
Gerade (g) and ungerade (u) Notations

The symmetry notation u and g are sometimes used
when describing molecular orbitals.
This refers to the operation of inversion, which requires
starting at an arbitrary point in the orbital, traveling
straight through the center, and then continuing outwards
an equal distance from the center.
The orbital is designated g (for gerade, even) if the phase
is the same, and u (for ungerade, uneven) if the phase
changes sign.
21
Inversion symmetry of orbitals
22
Molecular orbitals using d orbitals
23
Construction of molecular orbitals

Use all available valence orbitals from atoms
Classify according to symmetry ( with respect
to axis
From N AOs, build N MOs of symmetry
Similarly N MOs of symmetry. These occur in
degenerate pairs
In general, the energy of each type of orbital
increases with the number of inter-nuclear nodes
24
Molecular orbital diagram of

homonuclear diatomic molecule
25
Period 2 diatomic molecules

According to molecular orbital theory, orbitals are built
from all orbitals that have the appropriate symmetry. In
homonuclear diatomic molecules of Period 2, that means
that two 2s and two 2pz orbitals should be used. From these
four orbitals, four molecular orbitals can be built:
Four MO
With N atomic orbitals the molecule will have N molecular

orbitals, which are combinations of the N atomic orbitals.
26

Bond order: b =(n-n*)
n= number of electrons in the bonding orbital
n*= number of electrons in the antibonding orbital
Bond order:
The greater the bond order between atoms of a given
pair of elements, the shorter is the bond and the greater is
the bond strength.
27
Variation of orbital energies
28
Orbital energy level diagram upto N2
Bond order of N2 = 3
Note and * of mixed 2s
and 2pz character
G.S. Conf. of N2: 1g2 1u2 1u4 2g2

29
Orbital energy level diagram of O2
Bond order of O2 = 2
Paramagnetic
G.S. Conf. of O2: 1g2 1u2 2g2 1u4 1g2

30
Orbital energy level diagram of O2
Bond order of O2 = 2
Paramagnetic
G.S. Conf. of O2: 1g2 1u2 2g2 1u4 1g2

31

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Quantum Theory: Background

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Classical Mechanics: Consequences

Certain Phenomena were unexplainable ???

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Black Body: A perfect absorber and a perfect emitter:

Actual black bodies don't exist in nature

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Black body radiation-the phenomena

At constant T, Intensity increases as

Such solid black bodies, when heated to glowing emitted a

Observations: Two Radiations Law

[Wiens Displacement Law]

(, T) increases with increase in T.

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Blackbody Radiation: Explanation

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Energy density rises without

Oscillators of short wavelength

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Blackbody Radiation: Explanation

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Planck Radiation Distribution Law

c is speed of light, k is Boltzmanns constant and h is Plancks constant.

Planck proposed empirical formula

Planck expression reproduces the

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Planck Law: Success story

dE = (8hc/5) d [e(hc/kT) -1]-1

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The Magic of Plancks formula

Differentiate d/d = 0 for

dE = d = (8/4) (hc/) [e(hc/kT) -1]-1 d

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Failure of Classical Physics to Explain

Kinetic energy of emitted

K.E. should depend on the

For frequencies above the

The energy of the incident light

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Photoelectric Effect: Einstein Explanation

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CHEM F111 : General Chemistry

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Black body radiation (1860):

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Atomic Spectra: The phenomena

Comparatively simple spectra

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Mathematical explanation of Line Spectra of

n1 and n2 (n2>n1) are positive