You are on page 1of 42


Presented By:
Dr. Vatsala Soni

Heisenberg Uncertainty Principle
 In the world of very small particles, one cannot measure any
property of a particle without interacting with it in some way

 This introduces an unavoidable uncertainty into the result

 One can never measure all the

properties exactly

Werner Heisenberg (1901-1976)

Measuring the position and
momentum of an electron
 Shine light on electron and detect reflected

light using a microscope

Minimum uncertainty in position

is given by the wavelength of the

So to determine the position

accurately, it is necessary to use
light with a short wavelength

Measuring the position and momentum
of an electron (cont’d)
 By Planck’s law E = hc/λ, a photon with a short wavelength has a
large energy

 Thus, it would impart a large ‘kick’ to the electron

 But to determine its momentum accurately,

electron must only be given a small kick

 This means using light of long wavelength!

Fundamental Trade Off …
 Use light with short wavelength:

 accurate measurement of position but not


 Use light with long wavelength

 accurate measurement of momentum but not


Planck’s Distribution

• Energies are limited to discrete value

– Quantization of energy

E  nh , n  0,1,2,...
Max Planck
• Planck’s distribution
dE  d 
5 (e hc / kT  1)
• At high frequencies approaches the Rayleigh-Jeans

hc hc
(e hc / kT  1)  (1   ....)  1 
kT kT
• The Planck’s distribution also follows Stefan-
Boltzmann’s Las

Wave-Particle Duality
-The particle character of wave
• Particle character of electromagnetic radiation
– Observation :
• Energies of electromagnetic radiation of frequency v
can only have E = 0, h, v 2hv, …
(corresponds to particles n= 0, 1, 2, … with energy = hv)
– Particles of electromagnetic radiation : Photon
– Discrete spectra from atoms and molecules can be explained
as generating a photon of energy hn .
– ∆E = hv

Wave-Particle Duality
-The particle character of wave
• Photoelectric effect
– Ejection of electrons from metals when
they are exposed to UV radiation
– Experimental characteristic
• No electrons are ejected, regardless
of the intensity of radiation, unless UV electrons
its frequency exceeds a threshold
value characteristic of the metal.
• The kinetic energy of ejected
electrons increases linearly with the
frequency of the incident radiation
but is independent of the intensity of Metal
the radiation .
• Even at low light intensities, electrons
are ejected immediately if the
frequency is above threshold.

Wave-Particle Duality
-The particle character of wave
• Photoelectric effect
– Observations suggests ;
• Collision of particle – like projectile that carries energy
• Kinetic energy of electron = hν - Φ
Φ : work function (characteristic of the meltal)

energy required to remove a electron from the metal

to infinity
• For the electron ejection , hν > Φ required.

• In case hν < Φ , no ejection of electrons

Wave-Particle Duality
-The particle character of wave
• Photoelectric effect

Wave-Particle Duality
-The wave character of particles
• Diffraction of electron beam from metal
– Davison and Germer (1925)
– Diffraction is characteristic property of
– Particles (electrons) have wave like
properties !
– From interference pattern, we can get
structural information of a surface
LEED (Low Energy Electron Diffraction)

Wave Particle Duality
• De Brogile Relation
– Any particle traveling with a linear
momentum p haspwave
Matter wave: = mvlength
= h/l

– Macroscopic bodies have high

momenta (large p)
 small wave length
 wave like properties are not observed

Schrödinger equation

• 1926, Erwin Schrödinger (Austria)

– Describe a particle with wave function
– Wave function has full information about the

Time independent Schrödinger equation

for a particle in one dimension

Schrodinger Wave Equation
In 1926 Schrodinger wrote an equation that
described both the particle and wave nature of the e-
Wave function (Y) describes:
1. energy of e- with a given Y
2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.

Schrodinger Equation
General form

HY = E Y
H= T + V
: Hamiltonian

The Schrodinger equation:

Kinetic + Potential Total

energy energy energy

For a given U(x),

• what are the possible (x)?
• What are the corresponding E?

For a free particle, U(x) = 0, so
2 2
 (x)  Ae ikx k
Where k = 2
= anything real = any value from
0 to infinity

The free particle can be found anywhere, with
equal probability

 When ψ is a solution, so is Nψ

 We can always find a normalization const. such that the

proportionality of Born becomes equality

N 2  * dx  1

  dx  1
 * Normalization const. are
already contained in wave
  *
 dxdydz    d  1
 * function

 Energy of a particle is

 Acceptable energy can be found

by solving Schrödinger equation

 There are certain limitation in

energies of particles

The information in a wavefunction
 Simple case

 One dimensional motion, V=0

 2 d 2
 2
 E
2m dx

k 2 2
  Aeikx  Be ikx E

Probability Density

  A
2 2
  Ae ikx


 B
2 2
  Be  ikx


  4 A cos 2 kx
  2 Acos kx
Eigenvalues and eigenfucntions
 Eigenvalue equation

(Operator)(function) = (constant factor)*(same function)

̂  

Eigenfunction Eigenvalue

Solution : Wave function Allowed energy (quantization)

(operator correspond ing to observable )  (value of observable ) 

Quantum Mechanics and Atomic Orbitals
 The first orbital of all elements is spherical.

 Other orbitals have a characteristic shape and position as described

by 4 quantum numbers: n,l,ml,ms. All are integers except ms

 Principal Quantum Number (n): an integer from 1... Total # e in

a shell = n2.

 Angular quantum number (l). (permitted values l = 0 to n1):

the subshell shape.
 Common usage for l = 0, 1, 2, 3, 4, and use s, p, d, f, g,...
 Subshell described as 1s, 2s, 2p, etc.

 Magnetic quantum number,ml, (allowed l to +l )
directionality of an l subshell orbital.
 Total number of possible orbitals is 2l+1.

 E.g. s and p subshells have 1 & 3 orbitals,


 Spin quantum number,ms (allowed values 1/2). Due to

induced magnetic fields from rotating electrons.

 Pauli exclusion principle: no two electrons in an atom

can have the same four quantum numbers.

Permissible Quantum States

Orbital energies of the hydrogen atom.

Shapes of orbitals (electron
probability clouds)
 s orbitals are spherical (1).
 p orbitals are dumbbell shaped (3).
 d orbitals have four lobes (5).
 f orbitals are very complex (7).

Orbital Energies of Multielectron Atoms
 All elements have the same number of orbitals (s,p,
d, and etc.).
 In hydrogen these orbitals all have the same energy.
 In other elements there are slight orbital energy
differences as a result of the presence of other
electrons in the atom.
 The presence of more than one electron changes
the energy of the electron orbitals

Shape of 1s Orbital

Shape of 2p Orbital

Shape of 3d Orbitals


Electron Configuration

 The arrangement of electrons in an atom in the

ground state.
 Need to learn some simple rules or principles.

Rules are…

 Aufbau principle
 Pauli’s exclusion principle
 Hund’s Rule

Aufbau Principle
 German for building up.
 An electron occupies the lowest-energy orbital
that can receive it.
 In Hydrogen, the electron goes into the 1s orbital
because it’s the lowest energy orbital.

A general rule --
they arrange
themselves to have
the lowest possible
Ground State

Pauli Exclusion Principle
 No two electrons in the same atom can have the same
set of four quantum numbers.
 Each electron in the same atom has a unique set of
quantum numbers.

Hund’s Rule
Equivalent orbitals of equal
energy are each occupied by
one electron before any one
orbital is occupied by a
second electron.

Hund’s Rule (cont.)

All electrons in singly

occupied orbitals have
the same spin.

Writing Electron Configurations

Standard Notation
Number of electrons
of Fluorine in the sub level 2,2,5

1s 2 2s2 2p5


Thank You