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ATOMIC

STRUCTURE
Presented By:
Dr. Vatsala Soni

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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)


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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
light

So to determine the position


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

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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!

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Fundamental Trade Off …
 Use light with short wavelength:

 accurate measurement of position but not

momentum

 Use light with long wavelength

 accurate measurement of momentum but not

position

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Planck’s Distribution

• Energies are limited to discrete value


– Quantization of energy

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

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

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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

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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.

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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

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

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

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Wave Particle Duality
• De Brogile Relation
(1924)
– 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

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Schrödinger equation

• 1926, Erwin Schrödinger (Austria)


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

Time independent Schrödinger equation


for a particle in one dimension

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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.

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Schrodinger Equation
General form

HY = E Y
H= T + V
: Hamiltonian
operator

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The Schrodinger equation:

Kinetic + Potential Total


=
energy energy energy

For a given U(x),


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

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


The free particle can be found anywhere, with
equal probability

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Normalization
 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

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Quantization
 Energy of a particle is

quantized
 Acceptable energy can be found

by solving Schrödinger equation

 There are certain limitation in

energies of particles

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The information in a wavefunction
 Simple case

 One dimensional motion, V=0

 2 d 2
 2
 E
2m dx
Solution

k 2 2
  Aeikx  Be ikx E
2m

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Probability Density
B=0

  A
2 2
  Ae ikx

A=0

 B
2 2
  Be  ikx

A=B

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

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

̂  
Operator

Eigenfunction Eigenvalue

Solution : Wave function Allowed energy (quantization)

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


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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,...
respectively.
 Subshell described as 1s, 2s, 2p, etc.

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 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,


respectively.

 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.

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Permissible Quantum States

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Orbital energies of the hydrogen atom.

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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).

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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

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Shape of 1s Orbital

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Shape of 2p Orbital

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Shape of 3d Orbitals

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Elements
and
Their
Electronic
Configurations

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Electron Configuration

 The arrangement of electrons in an atom in the


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

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Rules are…

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

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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.

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

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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.

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

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Hund’s Rule (cont.)

All electrons in singly


occupied orbitals have
the same spin.

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Writing Electron Configurations

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

1s 2 2s2 2p5

Sublevels

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Thank You

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