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Structure of atoms

Modern Atomic Theory

As early as 400 B.C. Greek philosophers
proposed that all matter is composed of atoms

In 18th century Europe, the first chemists

noticed characteristics shared by all compounds

These observations of compounds and their

reactions led to three important laws:
Welcome to Atoms

Mukesh Sharma
After this lesson
Know more about the discovery of electron , proton
and neutron.
Thomson, Rutherford and Bohr atomic models.
Rutherfords Alpha scattering experiment.
Spectrum of elements
Quantum mechanical model of atom.
Orbital concept
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DPS Jodhpur The Chemophile
Believe it or not
this is a
microscope. Even
with the worlds
best microscopes
we cannot clearly
see the structure or
behavior of the
scientists rely upon models to help us to
understand the atom. Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Is this really an Atom?
Even though we do not know
what an atom looks like,
scientific models must be
based on evidence.

The model above represents

the most modern version of the
(Artist drawing) Mukesh Sharma

The Chemophil
Can a Model be Changed?
A model can be changed as new
information is collected.
From the early Greek concept to
the modern atomic theory,
scientists have built upon and
modified existing models of the
The Chemophile
Mukesh Sharma

460 BC Democritus develops the idea of atoms

he pounded up materials in his pestle and

mortar until he had reduced them to

smaller and smaller particles which he

(greek for indivisible)

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460 -370 BC Democritus develops the idea of atoms
he pounded up materials in his pestle and

mortar until he had reduced them to smaller

and smaller particles which he called

(greek for indivisible)

- First to propose idea of Atom

- Atom = a + tomos = cannot be cut
- Based solely on logic; not supported by experiment
(12 1500 CE)
Modern word Chemistry came from
Arabic word Al-kimiya
Recognized importance of
Responsible for developing Lab
equipments & procedures that still used
Galilio ~ 1600 CE
Birth of Modern Science combining logic with
experiments and publishing results.

Lavoisier & Priestly

1700s CE
Quantitative analysis of
Law of conservation of
mass: Matter can neither be
created nor destroyed
Law of Definite Proportions
A given compound contains the same
elements in exactly the same proportions
by mass, regardless of the size or source
of the sample
Law of Conservation of Mass
In a reaction, matter is neither
created or destroyed

Law of Multiple Proportions

When the same elements combine to
form different compounds, they do so
in mass ratios that can be expressed
by small whole numbers
Daltons Atomic Theory (1803)
Many fine maidens
are hot for me
because of my
ruggedly handsome
looks, boss sideburns,
and my atomic
Daltons Modern Atomic Theory
1. All matter is made of indivisible and
indestructible atoms.
2. All atoms of a given element are identical in
their chemical and physical properties
3. Atoms of different elements differ in their
chemical and physical properties.
4. Atoms of different elements combine in
simple whole number ratios to form
5. Chemical reactions consist of the
combination, separation, or rearrangement of
Daltons Modern Atomic Theory

2 Problems with his Theory:

Atoms of the same element have different

Atoms have subatomic particles (electrons,
protons and neutrons)

So, Daltons Theory is not completely correct.

Discharge Tube Experiment

William Crooks performed this exp. In cylindrical glass tube as

shown in figure.
Observations :
1. No current flows at 1 atm pressure even at high voltage (about
104 V )
2. When pressure is reduced to 10-2 atm, gas is found to emit light
which depends upon the nature of gas.
3. Further decrease in pressure stops emission of light but walls
opposite to cathode starts glowing and this is called
Result : Fluorescence is due to rays emitted from cathode and
hence these rays are called cathode rays.
Discovery of the Electron
In 1897, J.J. Thomson used a cathode ray tube
to deduce the presence of a negatively charged

Cathode ray tubes pass electricity through a gas

that is contained at a very low pressure.
Cathode ray tube

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Cathode ray tube

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Results of Cathode Ray Experiments

Electrons travel in straight lines

They have mass
They are invisible
They are independent of cathode composition
They bend in a magnetic field like a negatively-
charged particle would
Property of cathode rays

1. They were produced by the negative

electrode, or cathode
2. These are negatively charged
3. They travel in straight lines and cast
sharp shadows.
4. They have energy and can do work.
5. They were deflected by magnetic fields
6. They have mass
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Discovery of electrons

As cathode rays are made up of material particles which are

attracted towards the positively charged plate. So , cathode
rays consists of negatively charged particles and they were
named as Electrons.
As J.J.Thomson studied the properties of cathode rays which
led to the discovery of electrons so, its
J.J. Thomson who discovered electrons
e/m ratio of electron

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e/m ratio of electron
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He initially switched off both the fields

and noted the equilibrium position.
He then switched off the magnetic field and noted down the
deflection point of
the cathode rays in the presence of only electric field. He noted
down the deflection.
Then he applied the magnetic field in such a way that the
cathode rays were brought back to the equilibrium position.
Now at equilibrium position, the electric and magnetic force on
the charged particle are equal. Using the equations of motion
he calculated the velocity of the particle.
He then carried out the calculations to determine the specific
charge (e/m) ratio of the particles.

e/m = 1.75882 X 1011 coulomb (C)/kilogram

e/m ratio of electron
E Applied electric field
B Applied magnetic field
R Constant
Charge on electron)

e- charge = -1.60 x 10-19 C

Thomsons charge/mass of e- = -1.76 x 1011 C/kg
e -
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mass = 9.10 x 10 -31
Millikan Oil Drop Experiment

A fine spray of oil falls through a hole into a chamber

the drops can be observed.
The plates at the top and bottom of the chamber are
charged (the top plate is positive).
X-rays are shot onto the oil drops which causes the
drops to be negatively charged In the absence of
voltage, the force on the drops is determined by their
When a voltage is applied, negatively charged drops will
slow down, stop or begin moving upwards.
The behavior of the drop is determined by the applied
voltage and the charge on the oil drop.
Millikan used these measurements
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to determine that the
charges on the drops were multiples of 1.6 x 10-19 C.

1. Like cathode rays, these positive rays are deflected

by electric or magnetic fields, but in the opposite
direction from cathode rays.
2. Canal ray particles have e/m ratios many times smaller
than those of electrons,
3. due to their much greater masses.
When different elements
are in the tube,
positive ions with different e/m
ratios are observed.

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Conclusions from the Study of the
a) Cathode rays have identical properties
regardless of the element used to
produce them. All elements must contain
identically charged electrons.
b) Atoms are neutral, so there must be
positive particles in the atom to balance
the negative charge of the electrons
c) Electrons have so little mass that atoms
must contain other particles that account
for most of the mass
Conclusions from the Study of the
Eugen Goldstein in 1886 observed
what is now called the proton -
particles with a positive charge, and
a relative mass of 1 (or 1840 times
that of an electron)
1932 James Chadwick confirmed
the existence of the neutron a
particle with no charge, but a mass
nearly equal to a proton
Modern Cathode Ray Tubes

Television Computer Monitor

Cathode ray tubes pass electricity

through a gas that is contained at a
very low pressure.
Mass of the Electron

Mass of the
electron is
9.11 x 10-28 g

The oil drop apparatus

1916 Robert Millikan determines the mass

of the electron: 1/1840 the mass of a
hydrogen atom; has one unit of negative
Thomsons Atomic Model

Thomson believed that the electrons were like plums

embedded in a positively charged pudding, thus it was
called the plum pudding model.

plum pudding
J.J. Thomson model of Atom

In 1904, Thomson proposed that atom is a sphere of positively

charged particles in which negatively charged electrons are
embedded. Stability of atom was explained on the basis of
attraction between positively and negatively charged protons
and electrons respectively.
Drawbacks: One major drawback is that it could not explained
the Rutherfords Alpha Scattering Experiment , hence rejected.
Ernest Rutherfords
Gold Foil Experiment - 1911

Alpha particles are helium nuclei -

The alpha particles were fired at a thin
sheet of gold foil
Particles that hit on the detecting
screen (film) are recorded
oversaw Geiger and Marsden carrying out his
famous experiment.
they fired Helium nuclei at a piece of gold foil
which was only a few atoms thick.

they found that although most of them passed

through. About 1 in 10,000 hit

Ernest Rutherford Mukesh Sharma

(1908 Nobel Prize in Chemistry)

particle velocity ~ 1.4 x 107 m/s
(~5% speed of light)
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Rutherfords -Scattering Experiment
1.Most of the -particles passed through the gold
2.A small fraction of -particles was deflected by
small angles.
3.A very few -particles (~1 in 20,000)bounced
back, that is, were deflected by nearly 1800.
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The -particle experiment
Most of the mass and all of the
positive charge is concentrated
in a small region called the
nucleus .

There are as many electrons

outside the nucleus as there are
units of positive charge on the
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The nuclear atom
protons 1919

James Chadwick
neutrons 1932
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Rutherfords Model of the Atom

atomic radius ~ 100 pm = 1 x 10-10 m

nuclear radius ~ 5 x 10-3 pm = 5 x 10-15 m

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Rutherfords Findings
Most of the particles passed right through
A few particles were deflected
VERY FEW were greatly deflected
The nucleus is heavily dense

a) The nucleus is small
b) The nucleus is dense
c) The nucleus is positively
The Rutherford Atomic Model
Based on his experimental evidence:
The atom is mostly empty space
All the positive charge, and almost all the
mass is concentrated in a small area in
the center. He called this a nucleus
The nucleus is composed of protons and
neutrons (they make the nucleus!)
The electrons distributed around the
nucleus, and occupy most of the volume
His model was called a nuclear model
Subatomic Particles
Particle Charge Mass (g) Location

(e-) -1 9.11 x 10-28 orbit/Electron cloud

(p+) 1.67 x 10-24 Nucleus

(no) 0 1.67 x 10-24 Nucleus
Scale of Atoms
The heaviest atom has a mass of only 4.8 x 10-22 g
and a diameter of only 5 x 10-10 m.
Useful units:

1 amu (atomic mass unit) = 1.66054 x 10-24 kg

1 pm (picometer) = 1 x 10-12 m
1 (Angstrom) = 1 x 10-10 m = 100 pm = 1 x 10-8 cm
e = 1.602X10-19 Coulomb
Biggest atom is 240 amu and is 50 across.
Typical C-C bond length 154 pm (1.54 )
Prentice-Hall 2002 General Chemistry: Slide 56 of 25
Molecular models are 1 /inch or about 0.4 /cm
Chapter 2
The Atomic
Most of the mass of the
atom is in the nucleus
(protons and neutrons)
Electrons are found
outside of the nucleus (the
electron cloud)
Most of the volume of
the atom is empty space

q is a particle called a quark

About Quarks
Protons and neutrons are
NOT fundamental particles.

Protons are made of

two up quarks and
one down quark.
Neutrons are made of
one up quark and
two down quarks.

Quarks are held together

by gluons
Atomic Number
Atoms are composed of identical protons,
neutrons, and electrons
How then are atoms of one element different
from another element?
Elements are different because they contain
different numbers of PROTONS
The atomic number of an element is the
number of protons in the nucleus
# protons in an atom = # electrons
Atomic Number
Atomic number (Z) of an element is the
number of protons in the nucleus of each atom
of that element.

Element # of protons Atomic # (Z)

Carbon 6 6
Phosphorus 15 15

Gold 79 79
Mass Number
Mass number is the number of protons and
neutrons in the nucleus of an isotope.
Mass # = p+ + n0

Nuclide p+ n0 e- Mass #
Oxygen - 18 8 10 8 18
Arsenic - 75 33 42 33 75
Phosphorus - 31 15 16 15 31
Dalton was wrong about all
elements of the same type being
Atoms of the same element can
have different numbers of
Thus, different mass numbers.
These are called isotopes.

Frederick Soddy (1877-1956) proposed

the idea of isotopes in 1912
Isotopes are atoms of the same element having different
masses, due to varying numbers of neutrons.
Soddy won the Nobel Prize in Chemistry in
1921 for his work with isotopes and
radioactive materials.
Naming Isotopes
We can also put the mass
number after the name of the
Isotopes are atoms of the same element having
different masses, due to varying numbers of
Isotope Protons Electrons Neutrons Nucleus
(protium) 1 1 0

(deuterium) 1 1 1

Hydrogen-3 1 1 2

Atoms of an element with the same number of

protons but different numbers of neutrons

16 17 18
8 O 8 O 8 O

Most elements have more than one isotope

Atomic Masses
Atomic mass is the average of all the naturally
isotopes of that element.
Carbon = 12.011
Isotope Symbol Composition of % in nature
the nucleus
Carbon-12 12
C 6 protons 98.89%
6 neutrons

Carbon-13 13
C 6 protons 1.11%
7 neutrons

Carbon-14 14
C 6 protons <0.01%
8 neutrons
Upland Chemistry Summer 06 Schrempp Atomic Structure 68
Upland Chemistry Summer 06 Schrempp Atomic Structure 69
Upland Chemistry Summer 06 Schrempp Atomic Structure 70
Mass number
(p+ + no)

Atomic number
(number of p+)
Nuclear Symbols

Element symbol
Upland Chemistry Summer 06 Schrempp Atomic Structure 72
End of Rutherfords
Rutherfords new evidence allowed him to
propose a more detailed model with a
central nucleus.
He suggested that the positive charge was
all in a central nucleus. With this holding
the electrons in place by electrical

However, this was not the end of the story.

Bohr Theory
1913 Niels Bohr
studied under Rutherford at the
Victoria University in Manchester.
Bohr refined Rutherford's idea by
adding that the electrons were in
orbits. Rather like planets orbiting
the sun. With each orbit only able
to contain a set number of
Bohrs Atom

electrons in orbits

Cartoon courtesy of
In order to understand
current atomic theory
we must first understand
the properties of light

Light behaves both as

a wave and as a particle
Wave-Particle Duality
JJ Thomson won the Nobel prize for describing the
electron as a particle.
His son, George Thomson won the Nobel prize for
describing the wave-like nature of the electron.

electron is The
a particle! electron is
an energy
Dont you
Oh, go fly a
get sassy
with me, kite, you
Boy! old geezer!

The photoelectric effect. Incoming EM radiation on the left ejects

electrons, depicted as flying off to the right, from a substance. Only one
photon (a packet of light energy) can eject one electron. Therefore,
light acts like particles (Einstein, 1905) because of the photons
quantized energy nature. This differed from the description of EM
radiation by Maxwell (1865) which showed the infinite divisibility of
EM energy in physical systems.
Light is a form of

Electromagnetic Radiation
It exhibits wavelike behavior as it travel through space
Kinds of em radiation: x-rays, ultraviolet light,
infared light, microwaves, radio waves
Together, all of the types of em radiation form the

electromagnetic spectrum
The study of light led to the
development of the quantum
mechanical model.
Light is a kind of electromagnetic
Electromagnetic radiation includes
many kinds of waves
All move at 3.00 x 108 m/s ( c)
Parts of a wave

t Wavelength
Origin e

Parts of Wave
Origin - the base line of the energy.
Crest - high point on a wave
Trough - Low point on a wave
Amplitude - distance from origin to crest
Wavelength - distance from crest to crest
Wavelength - is abbreviated Greek
letter lambda.
The number of waves that pass a given
point per second.
Units are cycles/sec or hertz (Hz)

Abbreviated the Greek letter nu

c =
Frequency and wavelength
Are inversely related
As one goes up the other goes down.
Different frequencies of light is
different colors of light.
There is a wide variety of
The whole range is called a spectrum
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Frequency, Wavelength and Velocity
Frequency : no of times wave passes through
a given point in 1 sec
() in HertzHz or s-1.
Wavelength distance b/n two successive
crest or trough
() in metersm.
cm m nm A0 pm
(10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)

Velocity (c)2.997925 108 m s-1.

= c/
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Relation b/n wave length and frequency
Spectrum High
energy energy
Radio Micro Infrare Ultra X- Gamm
waves waves d . - Rays aRays
Low violet High
Frequency Frequency
Long Short
Wavelength Wavelength
Visible Light
Velocity The distance traveled by a
wave in one second is termed as its
velocity, it is generally denoted by the
letter 'c'.
Wave number It is the number of
wavelengths per centimeter.
It is equal to the inverse of a wavelength
expressed in centimeter.
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3. A radio station broadcasts on a frequency of
980 kHz (kilohertz). What is the
electromagnetic radiation broadcasted by the
radio station?

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Solution The frequency of the
radiation emitted is = 980 kHz = 980
x 103 Hz = 980 x 103 s-1 c = 3.0 x
108 ms-1
The radio station broadcasts
electromagnetic radiation of wavelength
= 306m

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Refraction of Light

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we are almost blind
I say we are almost blind because we are only
seeing about 1.5 percent of the whole
electromagnetic spectrum. Visible light is not
different than any of these other forms of
light except for the fact that our eyes
evolved to see this narrow slice because
thats the light region that our sun mostly

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Electromagnetic radiation propagates
through space as a wave moving at the
speed of light.

c =
C = speed of light, a constant (3.00 x 108 m/s)
= frequency, in units of hertz (hz, sec-1)
= wavelength, in meters
The energy (E ) of electromagnetic
radiation is directly proportional to the
frequency ( ) of the radiation.
E = h
E = Energy, in units of Joules (kgm2/s2)

h = Plancks constant (6.626 x 10-34 Js)

= frequency, in units of hertz (hz, sec-1)

Spectroscopic analysis of the visible spectrum

produces all of the colors in a continuous spectrum

Longer Wavelength, Lower Energy
Types of electromagnetic radiation:
= Wavelength Table
Low Frequency

High Frequency
Longer Wavelength

Higher Frequency and Energy

Electron transitions
involve jumps of
definite amounts of
energy (quanta).

This produces bands

of light with definite
Emission Spectrum

Continuous Emission Spectrum

Line Emission Spectrum (hydrogen)

1. Electron absorbs
energy from the flame
goes to a higher energy Light Photon

2. Electron goes back down to

lower energy state and releases
the energy it absorbed as light.
Flame Test for Cations

lithium sodium potassium copper

(i) The electrons are ejected from the metal
surface as soon as the beam of light strikes
the surface, i.e., there is no time lag between
the striking of light beam and the ejection of
electrons from the metal surface.
(ii) The number of electrons ejected is
proportional to the intensity or brightness of

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(iii) For each metal, there is a characteristic
minimum frequency,n
(also known as threshold frequency) below
which photoelectric effect is not observed. At
a frequency n >n

, the ejected electrons come out with certain

kinetic energy. The kinetic energies of these
electrons increase with the increase of
frequency of the light used.

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The Photoelectric Effect

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The Photoelectric Effect
At the stopping voltage the kinetic energy of the
ejected electron has been converted to potential.

mu2 = eVs

At frequencies greater than o:

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The Chemophile
The Photoelectric Effect
Wo = h o W0 = work function
Ephoton = Eke + w0 o =h
o = thresold frequen

Ek = Ephoton - w0
Ek = h - h o
Ek = h[ - o ]
Stopping electrical work = eV=ke= 1 mu2
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Answer on next slide

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Black body radiation

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The Chemophile
Dual Behaviour of Electromagnetic Radiation
The particle nature of light posed a dilemma
for scientists.

On the one hand, it

could explain the black body radiation and
photoelectric effect satisfactorily but on the other
hand, it was not consistent with the known wave
behaviour of light which could account for the
phenomena of interference and diffraction. The only
way to resolve the dilemma was to accept the idea that
light possesses both particle and wave-like properties,
i.e., light has dual behaviour. Depending on the
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experiment, we find that
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The Chemophile
the most important equation to come from Bohrs
model is the expression for the energy levels available
to the electron in the hydrogen atom:

The negative sign in Equation (7.1) simply means that

the energy of the electron bound to the nucleus is
lower than it would be if the electron were at an
distance from the nucleus, where there
is no interaction and the energy is

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Calculate the energy required to remove the electron
from a hydrogen atom in its ground state.

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Excitaion and transitions of

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The Chemophile
Emission and Absorption

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Atomic Spectrum

How color tells us about atoms

White light is
made up of all
the colors of
the visible
Passing it
through a prism
separates it.
If the light is not white
By heating a gas
or with
electricity we
can get it to give
off colors.
Passing this light
through a prism
does something
Atomic Spectrum
Each element
gives off its own
Can be used to
identify the
How we know
what stars are
made of.
These are
called line
unique to each
These are
emission spectra
Mirror images
are absorption
Light with black
An explanation of Atomic Spectra
Where the electron starts

When we write electron configurations we are

writing the lowest energy.
The energy level an electron starts from is
called its ground state.
Changing the energy
Lets look at a hydrogen atom
Changing the energy
Heat or electricity or light can
move the electron up energy levels
Changing the energy
May fall down in steps
Each with a different energy
The Bohr Ring Atom
Ultraviole Visible Infrared
Further they fall, more energy,
higher frequency.
This is simplified
the orbitals also have different
energies inside energy levels
All the electrons can move around.
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Wave length

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Energy-Level Diagram

E = EH EL =
nL2 nH2

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Ionization Energy of Hydrogen
1 1
E = RH ( 2 2 ) = h
ni nf

As nf goes to infinity for hydrogen starting in the ground state:

h = RH ( 2 ) = RH

This also works for hydrogen-like species such as He+ and Li2+.

h = -Z2 RH

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9-5 Two Ideas Leading to a New
Quantum Mechanics
Wave-Particle Duality.
Einstein suggested particle-like properties of
light could explain the photoelectric effect.
But diffraction patterns suggest photons are
deBroglie, 1924
Small particles of matter may at times
display wavelike properties.

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Niels Bohr won the Nobel Prize for his work.
However, the model only worked perfectly for
hydrogen. What about all of those other elements??

Louis de Broglie - Thought that if light, which was

thought to have wave characteristics, could also have
particle characteristics, then perhaps electrons, which
were thought to be particles, could have characteristics
of waves.

An electron in an atom was a standing wave!

02/03/17 149
deBroglie and Matter Waves

for electron

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and KE of particle of a particle
For any charged particle
KE= KE=QV = electrical wo
Q= is charge on particle
V= [i] v= potential difference

= [ii]

From [i] and [ii]


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Matter Waves

Louis de Broglie (1924) suggested that if waves can behave

like particles, maybe particles can behave like waves.
He proposed that electrons are waves of matter. The
reason for the size and number of electrons in a Bohr
electron shell is the number of wave periods that exactly
Heisenbergs Uncertainty Principle
Werner Heisenberg
German physicist, 1901-

Heisenberg wished to be
able to determine
precisely what the
position and momentum

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Werner Heisenberg - Developed the uncertainty
principle: It is impossible to make simultaneous and
exact measurements of both the position (location)
and the momentum of a sub-atomic particle such as
an electron.

( x)( p) h/4

Our knowledge of the inner workings of atoms and

molecules must be based on probabilities rather
than on absolute certainties.

02/03/17 154
Heisenbergs Uncertainty
Principle, 2
To see an electron and determine its
position it has to be hit with a photon
having more energy than the electron
which would knock it out of position.
To determine momentum, a photon of low
energy could be used, but this would give
only a vague idea of position.
Note: the act of observing alters the
thing observed.
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Heisenbergs Uncertainty
Principle, 3
Using any means we
know to determine
position and momentum,
the uncertainty of
position, q, and the
uncertainty of
momentum, p, are
q p h/2, where h is
Plancks constant

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Particles or Waves?

Question: Are the fundamental constituents of

the universe
Particles which have a position and
momentum, but we just cant know it,
Waves (of probability) which do not
completely determine the future, only make
some outcome more likely than others?

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Does Quantum Mechanics
describe Nature fully?
Einstein said
God does not
play dice.

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Schrdingers Wave Equations

In 1926, Erwin Schrdinger published a general theory of matter

Schrdingers equations describe 3-dimensional waves using
probability functions
Gives the probability of an electron being in a given place at a
given time, instead of being in an orbit
The probability space is the electron cloud.
The Quantum Mechanical Model
Energy is quantized. It comes in chunks.
Quanta - the amount of energy needed to move
from one energy level to another.
Quantum leap in energy.
Schrdinger derived an equation that described the
energy and position of the electrons in an atom
Treated electrons as waves

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The Quantum Mechanical Model
Does have energy levels
for electrons.
Orbits are not circular.
It can only tell us the probability of
an electron a certain distance from the nucleus.

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The Quantum Mechanical Model
The electron is found
inside a blurry electron
An area where there is a
chance of finding an
Draw a line at 90 %

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Erwin Schrdinger - Developed a form of quantum
mechanics known as wave mechanics.
H = Hamiltonian operator
E = Total energy of the system
Wave function

[(-h2)/(8 2m)] 2 - [e2/r] = E

Kinetic Energy Potential Energy
Term Term
This is simply a quantum mechanical statement of the Law
of Conservation of Energy
02/03/17 163
Of the numerous solutions to the Schrdinger equation
for hydrogen, only certain ones are allowed due to the
following boundary conditions:

, the wave function, must be continuous and finite.

It must be single-valued at all points (There cant be
two different probabilities of finding an electron at one
point in space).
The probability of finding the electron, 2, somewhere
in space must = 1.
- 2dxdydz = 1
Y has many values that meet these conditions. They are
called orbitals.
02/03/17 164
Wave Function - A mathematical function associated
with each possible state of an electron in an atom or

It can be used to calculate the energy of an

electron in the state

the average and most probable distance from the


the probability of finding the electron in any

specified region of space.
02/03/17 165
Azimuthal Quantum Number, l - The quantum
number that designates the subshell an electron
occupies. It is an indicator of the shape of an orbital
in the subshell. It has integer values from 0 to n-1.
l = 0, 1, 2, 3, , n - 1
s p d f
Magnetic Quantum Number, ml - The quantum
number that determines the behavior of an electron
in a magnetic field. It designates the orbital and
has integer values from -l to +l including 0. 0
ml = -l, , -3, -2, -1, 0, +1, +2, +3, , +l
02/03/17 166
Spin Quantum Number, (ms)
- The quantum number
that designates the orientation of an electron in a
magnetic field. Simply direction of spin
(i) Clock wise (ii) anti clockwise
It has half-integer values, + or -. Respectively

Representation of
electron and
orbital 167
Spin Quantum Number, (ms)
- (i) parallel spin (ii) anti parallel spin

Can not exist

magnetic field
repulsions ]

02/03/17 168
So what do atoms look like?
A. Interpretation of : The probability of finding
an electron in a small volume of space centered
around some point is proportional to the value of
at that point.
B. Electron Probability Density vs. r

C. Dot Density Representation: Imagine super-

imposing millions of photographs taken of an
electron in rapid succession.

D. Radial Densities
02/03/17 169
The Quantum Mechanical
Model of the Atom

Erwin Schroedinger attempted to describe an

electrons behavior by emphasizing the wave aspect
rather than the particle aspect.
this is the time independent Schroedinger equation
is the wave function, a function which gives the
amplitude of
the electron wave as a function of x, y, z, t

E is the energy operator V is the potential energy

The solution of the Schroedinger equation gives an
infinite number of solutions
(just as the Bohr model of the H atom gave an
infinite number of orbits). Each of these is called an
Mukesh Sharma
9-6 Wave Mechanics
Standing waves.
Nodes do not undergo displacement.

= , n = 1, 2, 3

Slide 171 of 50
The Chemophile
Wave Functions

, psi, the wave

Should correspond to a
standing wave within the
boundary of the system
being described.
Particle in a box.
2 n x

Slide 172 of 50
The Chemophile
Probability of
Finding an Electron

Slide 173 of 50
The Chemophile
Wave Functions for Hydrogen

Schrdinger, 1927 E = H

H (x,y,z) or H (r,,)

(r,,) = R(r) Y(,)

R(r) is the radial wave function.

Y(,) is the angular wave
Slide 174 of 50
The Chemophile
Bohrs Model of
the Atom (1913)
1. e- can only have specific
(quantized) energy
2. light is emitted as e-
moves from one energy
level to a lower energy
En = -RH ( )
n (principal quantum number) = 1,2,3,
RH (Rydberg constant) = 2.18 x 10-18J

The Wave-like Electron

The electron propagates

through space as an energy
wave. To understand the
atom, one must understand
the behavior of
electromagnetic waves.

Duuude! How you like my

new doo? Aint it a trip?

Louis deBroglie
Schrodinger Wave
Published in 1926, used the hypothesis that
electrons have a dual wave-particle nature;
Together with the Heisenberg Uncertainty
Principle, it laid the foundation for modern
quantum theory
Quantum Theory describes mathematically the
wave properties of electrons and other very
small particles
The Bohr Model of the Atom
I pictured
electrons orbiting
the nucleus much
like planets
orbiting the sun.
But I was
wrong! Theyre
more like bees WRONG!!!
around a hive.
Neils Bohr
Wave function equations only give the
probability of finding an electron at any given
place around the nucleus
They do not travel around the nucleus in neat
orbits. Instead they exist in orbitals
Orbital: A three-dimensional region around
the nucleus that indicates the probable location
of an electron.
Think of the 4
numbers as
where your
seat is in the
1. Level
2. Gate
3. Row
4. Seat
Pauli Exclusion Principle

No two electrons in an atom

can have the same four
quantum numbers.

And, no two fans in the

Superdome should have the
Wolfgang same 4 seat numbers!
Principal Quantum Number
Generally symbolized by n, it denotes the shell
(energy level) in which the electron is located.

Number of electrons
that can fit in a shell:

Angular Momentum Quantum
The angular momentum quantum number, generally
symbolized by l, denotes the orbital (subshell) in
which the electron is located.
Magnetic Quantum Number
The magnetic quantum number, generally
symbolized by m, denotes the orientation of the
electrons orbital with respect to the three axes in

Spin Quantum Number
Spin quantum number denotes the behavior
(direction of spin) of an electron within a magnetic

Possibilities for electron spin:

Assigning the Numbers
The three quantum numbers (n, l, and m) are
The principal quantum number (n) cannot be
n must be 1, 2, 3, etc.
The angular momentum quantum number (l) can
be any integer between 0 and n - 1.
For n = 3, l can be either 0, 1, or 2.
The magnetic quantum number (m) can be any
integer between -l and +l.
For l = 2, m can be either -2, -1, 0, +1, or
Principle, angular momentum, and magnetic quantum numbers: n,
l, and ml
An orbital is a region within an atom where there
is a probability of finding an electron. This is a
probability diagram for the s orbital in the first
energy level

Orbital shapes are defined as the surface that

contains 90% of the total electron probability.
Sizes of s orbitals
Orbitals of the same shape (s, for instance) grow
larger as n increases

Nodes are regions of low probability within an

Max Planck proposed the idea of quanta, small
specific amounts of energy.
The electron cloud is the region outside of the
nucleus where an electron can most probably be
The Pauli exclusion principle states that no two
electrons in the same atom can have the same four
quantum numbers
Hunds rule says that orbitals of equal energy are
each occupied by one electron of the same spin
before any is occupied by a second
Louis deBroglie believed that electrons could have a
dual wave-particle nature
The magnetic quantum number indicates the position
of an orbital about the three axes in space.
The photoelectric effect is the emission of electrons
from metals that have absorbed photons.
The wave model of light did not explain the
photoelectric effect. Only the particle model could.
The energy of a photon, or quantum, is related to its
Both the Heisenberg uncertainty principle and the
Schrodinger equation led to the concept of atomic
Quantum Numbers
Theangularmomentumquantumnumberhasthesymbol .

= 0, 1, 2, 3, 4, 5, .......
= s,p,d,f,g,h,.......(n1)

Magnetic Quantum Numbers


Valuesofm = - , (- .....0, .......,

representing the spatial [3d]

If=0(oranssubshell),thenm = 0.

If =1(orapsubhell),thenm = 1,0,+1. x
Spin quantum numberThe last quantum number
is the spin quantum number which has the
symbol ms.

Subshell, orbital and electron

s subshell p subshell d subshell f subshell

= 0 = 1 = 2 = 3

m= 0 m= -1, 0, +1 m= -2, -1, 0, +1, +2 m= -3, -2, -1, 0, +1,

+2, +3

Onesorbital Threeporbitals Fivedorbitals Sevenforbitals

Twoelectr Sixelectro
10electrons 14electrons
ons ns
Shell,subshell, orbital and
electron NO of
Shell l subshell ml Orbitals
1 0 1s 0 1 1

2 0 2s 0 1 4
1 2p -1, 0, +1 3

3 0 3s 0 1
1 3p -1, 0, +1 3 9
2 3d -2, -1, 0, +1, +2 5

4 16
etc. etc. etc. etc. etc.
Principle Shells and Subshells
Magnetic quantum
Principle electronic shell,m
n l= - l2,-2,
= 1, 3 -1, 0,
Angular momentum
1, 2+l quantum number,
l = 0, 1, 2(n-1)

l = 0, s
l = 1, p
l = 2, d
l = 3, f

The Chemophile Slide 198 of 50

Orbital Energies

Slide 199 of 50
The Chemophile
Interpreting and Representing the Orbitals of the Hydrogen

Slide 200 of 50
The Chemophile
Mukesh Sharma
s orbitals

Slide 202 of 50
The Chemophile
Mukesh Sharma
Mukesh Sharma

Mukesh Sharma
d Orbitals

Slide 206 of 50
The Chemophile

Mukesh Sharma
Prentice-Hall 2002 General Chemistry: Slide 208 of 50
Chapter 9
Prentice-Hall 2002 General Chemistry: Slide 209 of 50
Chapter 9
There are two types of nodes that can occur; angular and radial nodes

Aradial nodeis a circular ring Anangular nodeis a flat plane


Radial Probability density and radial node

At how many palces probability density is zero for

1s ,2p and 3d
What should be for 4f

Empirically by observing the plots for the various

probability density functions
we say that the number of radial nodes for a given orbital
= n-l -1
radial nodes for a given orbital = n-l
Q 1 Find no of radial node
Q 2 if n=3 what is l =
Q 3 what can other possible set of
n and l to have same graph

A1 - 2i.e 3s

A2 - l=2
A 3 - 4p ,5d ,6f
Angular nodes [nodal plane ]

For p orbital For d orbital

l =1 l =2
Nodal plane = l Nodal plane = 2
Number of nodal plane [angular nodes ] for an orbital = l

Number of radial node [spherical nodes ] =n-l-1

Total Number of nodes =n-l-1+ l =n-1
Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Mukesh Sharma
Penetrration power

Z eff = Z - electron screening

inner shell electrons are able to screen part or all of the
nuclear charge, but this screening is offset by orbital
penetration. ns > np > nd > nf
Mukesh most penetration
Sharma least
9-11 Electron Configurations

Aufbau process.
Build up and minimize energy.
(n+l )rule
Pauli exclusion principle.
No two electrons can have all four quantum
numbers alike.
Hunds rule.
Degenerate orbitals are occupied singly first.
Half filled subshell statbility

Prentice-Hall 2002 General Chemistry: Slide 224 of 50

Chapter 9
Electronic distribution in Mg

in shells K L
8 2
in subshells 1s 2s 2p 3s
2 2 6 2

in orbitals

1s 2s 2p 3s
Electron Configurations
The way electrons are arranged in atoms. Follow the following rules
1 Aufbau principle-
electrons enter the lowest energy subshell first.
This causes difficulties because of the overlap of subshells of different energies.
2 n+l rule-
(i) lower n+l of subshell lower energy
Example 3d or 4s which is filled first
Ans 4s first because its n+l is 4+0=4 which is lower than 3+2=5 for 3d
(ii) Incase of same n+l of two or more subshell , the one with lower n has lower energy
and filled first
Example 4d or 5p which is filled first
Ans 4d first as its n is lower n+l is 4+2=6 and =5+1 for 5p but 4 is lower
3 Hunds rule
4 Pauli Exclusion Principle
5 Stability of half filled and fullfilled subshells
7s 7p
6s 6p 6d
5s 5p 5d
Increasing energy

4s 4p 4d 4f

3s 3p 3d

2s 2p

Based on n value- is this correct s

1s Ans no because energy depend o
7s 7p
6s 6p 6d
5s 5p 5d 5f
Increasing energy

4s 4p 4d 4f

3s 3p 3d

2s 2p

Based on n +l
7s 5f
Increasing energy



Electron Configuration
4 Hunds Rule- When electrons occupy orbitals of
equal energy [orbital of same subshell ] they dont
pair up until each orbital has single electron with
same spin .
Lets determine the electron configuration for
1s 2s 2p

1s 2s 2p

Last is Correct
1s 2s 2p
7p 6d
7s 6p 5f
6s 5p 4f
Increasing energy

4s 3d
3p The first two electrons go
3s into the 1s orbital
2p Notice the opposite spins
2s only 13 more

7p 6d
7s 6p 5f
6s 5p 4f
Increasing energy

4s 3d
3p The next electrons go
3s into the 2s orbital
2p only 11 more

7p 6d
7s 6p 5f
6s 5p 4f
Increasing energy

4s 3d
3p The next electrons
go into the 2p
2s orbital
only 5 more
7p 6d
7s 6p 5f
6s 5p 4f
Increasing energy

4s 3d
3p The next electrons
go into the 3s
2s orbital
only 3 more
7p 6d
7s 6p 5f
6s 5p 4f
Increasing energy

4s 3d
3p The last three
3s electrons go into the
2p 3p orbitals.
2s They each go into
separate shapes
1s 3 unpaired electrons
Rule 4 Pauli Exclusion Principle
Lets determine the electron
configuration for 2He


The easy way to remember

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s 2
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s 4
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s 12 electrons
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2
3s 3p 3d
2s 2p
1s 20 electrons
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2 3d10 4p6
3s 3p 3d 5s2
2s 2p
1s 38 electrons
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2 3d10 4p6
3s 3p 3d 5s2 4d10 5p6 6s2
2s 2p
1s 56 electrons
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2 3d10 4p6
3s 3p 3d 5s2 4d10 5p6 6s2
2s 2p 14 10
4f 5d 6p 7s 6 2
1s 88 electrons
Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2 3d10 4p6
3s 3p 3d 5s2 4d10 5p6 6s2
2s 2p 14 10
4f 5d 6p 7s 6 2
1s 14 10 6
5f 6d 7p
118 electrons
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10
6 2 14 10 6 2 14 10 6
5p 6s 4f 5d 6p 7s 5f 6d 7p

Group the energy levels together

1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14
2 6 10 14 2 6 10 2 6
5s 5p 5d 5f 6s 6p 6d 7s 7p
Exceptions to Electron Configuration
Orbitals fill in order
Lowest energy to higher energy.
Adding electrons can change the energy of the
Filled and half-filled orbitals have a lower
Makes them more stable.
Changes the filling order of d orbitals
Write these electron
Titanium - 22 electrons

1s22s22p63s23p64s2 3d2
Vanadium - 23 electrons

1s22s22p63s23p64s2 3d3
Chromium - 24 electrons

1s22s22p63s23p64s2 3d4 is expected

But this is wrong!!
Rule 5 Stability of half filled and fullfilled

Chromium is actually
This gives us two half filled orbitals.
Chromium is actually

This gives us two half filled orbitals.
Chromium is actually
This gives us two half filled orbitals.

4s1 3d5
lower in energy.
The same principle applies to
Coppers electron configuration
Copper has 29 electrons so we expect
But the actual configuration is
This gives one filled orbital and one half filled
Remember these exceptions
d4s2 d5 s1
d9s2 d10s1
In each energy level
The number of electrons that can fit in each
energy level is calculated with
Max e- = 2n2 where n is energy level


Quantum Numbers
Each electron in an atom has a unique set of 4
quantum numbers which describe it.

1. Principal quantum number

2. Angular momentum quantum number
3. Magnetic quantum number
4. Spin quantum number
The s orbital has a spherical shape centered around
the origin of the three axes in space.

s orbital shape
P orbital shape
There are three dumbbell-shaped p orbitals in
each energy level above n = 1, each assigned to
its own axis (x, y and z) in space.
Things get a bit more
complicated with the five d
d orbital shapes
orbitals that are found in
the d sublevels beginning
with n = 3. To remember
the shapes, think of double

and a dumbell
with a donut!
Shape of the f orbital
Orbital Subshells
Subshell # of orbitals e- in each total e-
s 1 2 2
p 3 2 6
d 5 2 10
f 7 2 14
# of
Energy Level Sublevel Orbitals

1 s 1 2

s 1 2
p 3 6

s 1 2
3 p 3 6
d 5 10
s 1 2

4 p 3 6
d 5 10
f 7 14
A maximum of two electrons
can occupy each orbital.
Each electron must have
different spin quantum
Hunds Rule
The most stable
arrangement of electrons
is that with the most
unpaired electrons all
with the same spin
Electrons in an atom will
occupy the lowest-energy
orbitals available
(aufbau = building up)
Writing Electron
1.Determine the number of
electrons and atom has
2. Fill orbitals in order of
increasing energy
Orbital filling table
Orbital Filling Order
A. General Rules

Pauli Exclusion Principle

Each orbital can hold TWO electrons with
opposite spins.
A. General Rules

Hunds Rule
Within a sublevel, place one e- per orbital
before pairing them.
Empty Bus Seat Rule

A. General Rules

Aufbau Principle
Electrons fill the
lowest energy
orbitals first.
Lazy Tenant
Orbital Diagrams
Orbital Diagrams are models of
electron arrangements showing
configuration, subshell, aufbau,
hunds, and pauli

H: [ ]
Orbital Diagrams
He: [ ]

Li: [ ] [ ]
1s 2s
B. Notation
Orbital Diagram

8e- 1s 2s 2p
Electron Configuration

1s 2s 2p
2 2 4
Practice Problems
1. Write the electron
configuration and orbital
diagram for B
Practice Problems
1.Write the electron
configuration and orbital
diagram for B
1s 2s 2p
2 2 1
C. Periodic Patterns
Example - Hydrogen

1s 1 1st column
of s-block

1st Period s-block

Practice Problems
1.Write the electron
configuration and orbital
diagram for P
Practice Problems
1.Write the electron
configuration and orbital
diagram for P
1s 2s 2p 3s 3p
2 2 6 2 3
Practice Problems
1.Write the electron
configuration and orbital
diagram for Sc
Practice Problems
1.Write the electron
configuration and orbital
diagram for Sc
1s 2s 2p 3s 3p 4s 3d
2 2 6 2 6 2 1
Practice Problems
1.Write the electron
configuration and orbital
diagram for Pr
Practice Problems
1.Write the electron
configuration and orbital
diagram for Pr
1s 2s 2p 3s 3p 4s 3d 4p 5s
2 2 6 2 6 2 10 6 2

4d10 5p6 6s2 4f3

B. Notation

Longhand Configuration
S 16e 1s2 2s2 2p6 3s2 3p4

Core Electrons Valence Electrons

Shorthand Configuration

S 16e- [Ne] 3s2 3p4

C. Periodic Patterns

Shorthand Configuration
Go up one row and over to the Noble Gas.
On the next row, fill in the # of e- in each



C. Periodic Patterns

Example - Germanium

[Ar] 4s 3d 4p 2 10 2
D. Stability

EXPECT: [Ar] 4s2 3d9

ACTUALLY: [Ar] 4s1 3d10

Copper gains stability with a full

D. Stability

Electron Configuration Exceptions

EXPECT: [Ar] 4s2 3d4

ACTUALLY: [Ar] 4s1 3d5

Chromium gains stability with a half-full d-

Electronic Structure of Atoms
Shells and

Shells of an
atom contain a
number of
Electronic Structure of Atoms
s p d f
Relative Energies for
Shells and Orbitals 7
Some orbital subshells 5
overlap others in
different energy levels.

of the
1 orbitals
2.7 PT and Electron Configuration
The First 20 elements: 1s
+ +
Li=1s22s1 2p
C=1s22s22p2 + +
O=1s22s22p4 3s
Ne=1s22s22p6 3p
Electronic Structure of Atoms
The First 10 elements: 1s
+ +
Li=1s22s1 2p