Chapter 2

“Atomic Structure”

GVHSS, AYYANTHOLE
 HISTORY OF THE ATOM

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 called

ATOMA
(greek for indivisible)
 HISTORY OF THE ATOM

1808 John Dalton

suggested that all matter was made up of

tiny spheres that were able to bounce around

with perfect elasticity and called them

ATOMS
 HISTORY OF THE ATOM

1898 Joseph John Thompson

found that atoms could sometimes eject a far

smaller negative particle which he called an

ELECTRON
In 1897, J.J. Thomson used a cathode ray
tube to deduce the presence of a negatively
charged particle: the electron
1. The cathode rays start from cathode and
move towards the anode.

2. These rays themselves are not visible

but their behaviour can be observed
with the help of certain kind of materials
(fluorescent or phosphorescent) which
glow when hit by them.
3. In the absence of electrical or magnetic
field, these rays travel in straight lines.
4. In the presence of electrical or
magnetic field, the behaviour of
cathode rays are similar to that
expected from negatively charged
particles, suggesting that the cathode
rays consist of negatively charged
particles, called electrons.
5. The characteristics of cathode rays
(electrons) do not depend upon the
material of electrodes and the nature of
the gas present in the cathode ray tube.

 Thus, we can conclude that electrons

are basic constituent of all the atoms.
 In1897, British physicist J.J. Thomson
measured the ratio of electrical charge
(e) to the mass of electron (me ) by using
cathode ray tube and applying electrical
and magnetic field perpendicular to each
other as well as to the path of electrons.
 Greater the magnitude of the charge on
the particle, greater is the deflection.
 Lighter the particle, greater the
deflection.
 Greater the magnitude of electrical or
magnetic field, greater the deflection.
 When only electric field is applied, the
electrons deviate from their path and hit
the cathode ray tube at point A. Similarly
when only magnetic field is applied,
electron strikes the cathode ray tube at
point C. By carefully balancing the
electrical and magnetic field strength, it
is possible to bring back the electron to
the path followed as in the absence of
electric or magnetic field and they hit the
screen at point B.
 Bycarrying out accurate measurements
on the amount of deflections observed by
the electrons on the electric field
strength or magnetic field strength,
Thomson was able to determine the
value of e/me as:

 e/m = 1.758820 × 1011 C kg–1

 Television Computer Monitor

Cathode ray tubes pass electricity

through a gas that is contained at a
very low pressure.
 Mass of the
electron is
9.11 x 10-28 g

The oil drop apparatus

1916 – Robert Millikan determines the mass

and charge of the electron
 He found that the charge on the electron
to be – 1.6 × 10–19 C. The present
accepted value of electrical charge is
–1.6022 × 10–19 C. The mass of the
electron (me) was determined by
combining these results with Thomson’s
value of e/me ratio.

me = e/(e/me)
= 9.1094×10–31 kg
 Electrical
discharge carried out in the
modified cathode ray tube led to the
discovery of particles carrying positive
charge, also known as canal rays.
 the positively charged particles depend
upon the nature of gas present in the
cathode ray tube. These are simply the
positively charged gaseous ions.
 The charge to mass ratio of the particles
is found to depend on the gas from which
these originate.
 Some of the positively charged particles
carry a multiple of the fundamental unit
of electrical charge.
 The behaviour of these particles in the
magnetic or electrical field is opposite to
that observed for electron or cathode
rays.
 The smallest and lightest positive ion was
obtained from hydrogen and was called
proton.
 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
Particle Absolute Relative Mass (g)
Charge Charge
Electron -1.6022x10-19 -1 9.11 x 10-28
(e-)

Proton +1.6022x10-19 +1 1.673 x 10-24

(p+)
Neutron 0 0 1.675 x 10-24
(no)
 J. J. Thomson
Thomson believed that the electrons
were like plums embedded in a
positively charged “pudding,” thus it
was called the “plum pudding” model.
 J. J. Thomson, in
1898, proposed that an
atom possesses a spherical shape (radius
approximately 10–10 m) in which the
positive charge is uniformly distributed.
The electrons are embedded into it in
such a manner as to give the most stable
electrostatic arrangement
 Thismodel considers that the mass of the
atom is assumed to be uniformly
distributed over the atom. Although this
model was able to explain the overall
neutrality of the atom, it could not explain
any other properties of atom.
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
 Most of the particles passed right through
 A few particles were deflected
 VERY FEW were greatly deflected

Conclusions:
a) The nucleus is small
b) The nucleus is dense
c) The nucleus is positively
charged
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”
• Size of the nucleus is very very small.
 The positive charge and most of the mass
of the atom is concentrated in extremely
small region, called nucleus.
 The nucleus is surrounded by electrons
that move around the nucleus with a very
high speed in circular paths called
orbits.
 Electrons and the nucleus are held
together by electrostatic forces of
attraction.
 When an electron is moving in an orbit, it
undergoes acceleration (because of
changing direction). According to the
electromagnetic theory of Maxwell,
charged particles when accelerated
should emit electromagnetic radiation
 Therefore an electron in an orbit will emit
radiation and as a result the radius of
orbit will continue to shrink. This may
lead to the falling of electron into the
nucleus. But this does not happen. Thus,
the Rutherford model cannot explain the
stability of an atom.
 This model also failed to explain the
arrangement of electrons around the
nucleus.
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 is the sum 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
 Contain the symbol of the element,
the mass number and the atomic
number.
Superscript →
Mass
number

Subscript →
Atomic
number
X
Dalton was wrong about all
elements of the same type being
identical
Atoms of the same element can
have different numbers of
neutrons.
Thus, different mass numbers.
These are called isotopes.
FrederickSoddy (1877-1956)
proposed the idea of isotopes in
1912
 Isotopesare 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.
Isotopes are atoms of the same element having
different masses, due to varying numbers of
neutrons.
Isotope Protons Electrons Neutrons Nucleus
Hydrogen–1
(protium) 1 1 0
Hydrogen-2
(deuterium) 1 1 1

Hydrogen-3 1 1 2
(tritium)
Elements
occur in
nature as
mixtures of
isotopes.
Isotopes are
atoms of the
same element
that differ in
the number of
neutrons.
 Isobars are the atoms with same mass
number but different atomic number
 For example, 14C and 14N.
 On the other hand,
 Atoms with identical atomic number but
different atomic mass number are known
as Isotopes.
 Isotopes have same chemical
properties but different physical
properties.
 Dual character of electromagnetic
radiation
 Experimental data regarding Atomic
Spectra
 Dual character of
electromagnetic radiation

 Wave nature of electromagnetic radiation

 Particle nature of electromagnetic radiation
 Wave nature of
electromagnetic radiation
 James Maxwell (1870) suggested that when
electrically charged particle is accelerated,
alternating electrical and magnetic fields
are produced and transmitted. These fields
are transmitted in the forms of waves called
electromagnetic waves or electromagnetic
radiation.
 The electric and magnetic fields are
perpendicular to each other and both are
perpendicular to the direction of
propagation of the wave.
 Electromagnetic waves do not require
medium and can move in vacuum.
 They differ from one another in wavelength
 They travel at the same speed, that of light
(3x108 m/s)
 The frequency (ν ) and wavelength (λ) are
used to represent them.
c = ν λ c- Velocity of light
Electromagnetic Radiations
 Particle Nature of
Electromagnetic Radiations
 Diffraction, interference etc. could be explained by the
wave nature of radiation. But they could not explain
 Black body radiation
 Photo-electric effect
 Variation of heat capacities of solids as a function of
temperature
 Line spectra of atom
 The first concrete explanation for the
phenomenon of the black body radiation was
done by Max Planck in 1900.
 When an iron rod is heated, it first turns to
dull red and then becomes more and more
red. As this is heated further, the radiation
emitted becomes white and then becomes
blue as the temperature becomes very high.
 Frequency of the radiation emitted goes from
a lower frequency to a higher frequency as
the temperature increases.
 The ideal body, which emits and absorbs all
frequencies, is called a black body and the
radiation emitted by such a body is called
black body radiation.
 T2>T1
intensity

T2

T1

Wave length
 At a given temperature, intensity of
radiation emitted increases with decrease of
wavelength, reaches a maximum value at a
given wavelength and then starts decreasing
with further decrease of wavelength.
 The above experimental results cannot be
explained satisfactorily on the basis of the
wave theory of light.
 Quantized Energy and Photons

• Planck: energy can only be absorbed or released

from atoms in certain amounts called quanta.
• The relationship between energy and frequency is
E  h 
where h is Planck’s constant (
6.626  10-34 J s ) .
 With this theory, Planck was able to explain
the distribution of intensity in the radiation
from black body as a function of frequency
or wavelength at different temperatures.
Photoelectric Effect
 In 1887, H. Hertz performed an experiment
in which electrons (or electric current) were
ejected when certain metals (for example
potassium, rubidium, caesium etc.) were
exposed to a beam of light. The
phenomenon is called Photoelectric
effect.
 The results observed in this experiment were:
 The electrons are ejected from the metal surface as
soon as the beam of light strikes the surface.
 The number of electrons ejected is proportional to
the intensity or brightness of light.
 For each metal, there is a characteristic minimum
frequency,ν0 (also known as threshold
frequency) below which photoelectric effect is
not observed.
 At a frequency ν >ν0, 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.
 All the above results could not be explained
on the basis of laws of classical physics.
 According to latter, the energy content of
the beam of light depends upon the
brightness of the light. In other words,
number of electrons ejected and kinetic
energy associated with them should depend
on the brightness of light.
 Einstein (1905) was able to explain the
photoelectric effect using Planck’s quantum theory
of electromagnetic radiation
 A beam of light can be viewed as shooting a beam
of particles, the photons. During a collision, the
photon transfers its energy instantaneously to the
electron and the electron is ejected without any
time lag. Greater the energy possessed by the
photon, greater will be transfer of energy to the
electron and greater the kinetic energy of the
ejected electron.
 if hν is the energy of the photon and hν0 the
minimum energy required to eject the
electron , then the difference in energy (hν –
hν0) is transferred as the kinetic energy of
the photoelectron.
 hν = hν0 +1/2 mev2
 Me is the mass of electron
 V is the velocity of the ejected electron
 Dual Behaviour of
Electromagnetic Radiation
 Particle nature 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.
 Atomic spectra
 Ordinary white light consists of waves with all the
wavelengths in the visible range, a ray of white light is
spread out into a series of coloured bands called
spectrum. Such a spectrum is called continuous
spectrum.
 The spectrum of radiation emitted by a substance that
has absorbed energy is called an emission spectrum.
 Absorption spectrum is the missing wavelength
which corresponds to the radiation absorbed by the
matter, leave dark spaces in the bright continuous
spectrum
Atomic spectra
 Emission Spectrum

The spectrum of radiation emitted by a substance that has

absorbed energy is called an emission spectrum.
Line Spectra of
Hydrogen Atom
Line Spectra of Hydrogen Atom

 Lyman series
 Balmer series
 Paschen series
 Brackett series
 Pfund series
 Series n1 n2 Region
Lyman 1 2,3….. Ultraviolet
Balmer 2 3,4……… Visible
Paschen 3 4,5……… Infrared
Brackett 4 5,6…….. Infrared
Pfund 5 6,7……… Infrared
 Rutherfords model is in trouble: an
“accelerated charge” should fall into nucleus

• Bohr revised Rutherford’s model to explain

the existence of line spectra for elements…
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
electrons.
Bohr’s Atom

electrons in orbits

nucleus
 HELIUM ATOM
Shell
proton

+
N
-
+
- N

electron neutron
 Bohr suggests that electrons can only exist in
certain orbits
 Line
spectrum result from the release of
photons as electrons fall back to lower orbit
 BOHR’S MODEL
FOR HYDROGEN ATOM
 POSTULATES
 The electron in the hydrogen atom can
move around the nucleus in a circular path
of fixed radius and energy. These paths are
called orbits, stationary states or allowed
energy states. These orbits are arranged
concentrically around the nucleus.
 The energy of an electron in the orbit does
not change with time. However, the electron
will move from a lower stationary state to a
higher stationary state when required
amount of energy is absorbed and energy is
emitted when electron moves from higher
stationary state to lower stationary state.
The energy change does not take place in a
continuous manner.
 The frequency of radiation absorbed or
emitted when transition occurs between two
stationary states that differ in energy by ΔE,
is given by :
 ν= ΔE/h= (E1 - E2)/h
 Where E1 and E2 are the energies of the
lower and higher allowed energy states
respectively.
 It is commonly known as Bohr’s frequency
rule.
 The angular momentum of an electron in a
given stationary state can be expressed as in
equation
 mev r= n.h/2∏ where n=1,2,3…….
Features of Bohr’s Model of atom
 The stationary states for electron are
numbered n = 1,2,3.......... These integral
numbers are known as Principal quantum
numbers.
 The radii of the stationary states are
expressed as :
 rn = n2 a0
 where a0 = 52.9 pm.
 The energy of stationary state is given by the
expression.
 En=-RH.(1/n2)
 RH is called Rydberg constant (2.18×10–18 J)
 n-Principal quantum number
 Explanation of
Line Spectrum of Hydrogen
 Energy absorbed or emitted is equal to:
ΔE = Ef – Ei
Ef and Ei are final and initial energy levels.
ΔE = [-RH/(nf )2] -[-RH/(ni)2]
= RH{[1/(ni)2]–[1/(nf )2]}
ν= ΔE/h
= RH{[1/(ni)2]–[1/(nf )2]}/h
ν is the frequency of radiation emitted or absorbed
 Limitations of Bohr’s Model
 It fails to account for the finer details (doublet, that
is two closely spaced lines) of the hydrogen atom
spectrum observed.
 This model is also unable to explain the spectrum of
atoms other than hydrogen.
 Bohr’s theory was also unable to explain the
splitting of spectral lines in the presence of
magnetic field (Zeeman effect) or an electric field
(Stark effect).
 It could not explain the ability of atoms to form
molecules by chemical bonds.
 TOWARDS QUANTUM MECHANICAL
MODEL OF THE ATOM
 Two important developments which
contributed significantly in the formulation
of such a model were :
1. Dual behaviour of matter,
2. Heisenberg uncertainty principle.
 The Wave Behavior of Matter
• Knowing that light has a particle nature, it seems
reasonable to ask if matter has a wave nature.
• Using Einstein’s and Planck’s equations, de Broglie
showed:
h

mv
• The momentum, mv, is a particle property, whereas
 is a wave property.
• de Broglie summarized the concepts of waves and
particles, with noticeable effects if the objects are
small.
 Energy and Matter
Size of Particle Wave
Matter Property Property
Large –
Mainly Unobservable
macroscopic
Intermediate –
Some Some
electron
Small –
Few Mainly
photon
The Uncertainty Principle
 It is impossible to determine simultaneously, the
exact position and exact momentum (or velocity)
of an electron.
 Δx. Δp ≥ h/4∏
 Δx . Δ(mv ) ≥ h/4∏
Δx is the uncertainty in position
And Δpx ( or Δvx) is
the uncertainty in momentum
Significance of Uncertainty Principle
 It rules out existence of definite paths or
trajectories of electrons and other
similar particles. Hence these are
replaced by probability of finding
electron
 The effect of Heisenberg Uncertainty
Principle is significant only for motion
of microscopic objects and is negligible
for that of macroscopic objects.
 Reasons for the Failure of
the Bohr Model
 It did not considered the wave character of
electron.
 It contradicts Heisenberg uncertainty
principle.
Quantum Mechanical Model
 The branch of science that
takes into account the dual
behaviour of matter is
called quantum mechanics.
 Quantum mechanics was
developed independently in
1926 by Werner Heisenberg
and Erwin Schrödinger.
 Quantum Mechanics and Atomic Orbitals

• Schrödinger proposed an equation that

contains both wave and particle terms.
^
H  E  E is energy &H is a
mathematical operator called Hamiltonian
• Solving the equation leads to wave functions.
• The wave function ψ gives the shape of the
electronic orbital. [“Shape” really refers to
density of electronic charges.]
• The square of the wave function, gives the
probability of finding the electron (electron
density)
 Quantum Mechanics and Atomic Orbitals
Solving Schrodinger’s
Equation gives rise to
‘Orbitals.’
These orbitals
provide the electron
density distributed
about the nucleus.
Orbitals are described
by quantum numbers.
 Quantum Mechanics and Atomic Orbitals
Orbitals and Quantum Numbers
• Schrödinger’s equation requires 3 quantum
numbers:
1. Principal Quantum Number, n. This is the
same as Bohr’s n. As n becomes larger, the atom
becomes larger and the electron is further from
the nucleus. It determines the size and energy
of the orbital. n = 1 , 2 , 3 , 4 , …. Represents
shells K,L,M,N….
 2. Azimuthal Quantum Number, l. This
quantum number depends on the value of n.
The values of l begin at 0 and increase to (n -
1). We usually use letters for l (s, p, d and f for
l = 0, 1, 2, and 3). Usually we refer to the s, p,
d and f-orbitals. It represents shape of the
orbital.
 n=1, l=0
 n=2, l=0,1
 n=3, l=0,1,2
 n=4, l=0,1,2,3
 3. Magnetic Quantum Number, ml. This
quantum number depends on l . The magnetic
quantum number has integral values between -
l and + l . Magnetic quantum numbers give
the 3D orientation of each orbital.
l=0, ml =0
l=1, ml =+1,0,-1
l=2, ml =+2,+1,0,-1,-2
l=3, ml =+3,+2,+1,0,-1,-2,-3
 Three quantum numbers are not enough to
explain the line spectra observed in the case of
multi-electron atoms, that is, some of the lines
actually occur in doublets (two lines closely
spaced), triplets (three lines, closely spaced)
etc. This suggests the presence of a few more
energy levels than predicted by the three
quantum numbers.
 In 1925, George Uhlenbeck and Samuel
Goudsmit proposed the presence of the fourth
quantum number known as the electron spin
quantum number (ms).
Electron spin quantum number (ms).
 Spin angular momentum of the electron can have
two orientations relative to the chosen axis. These
two orientations are distinguished by the spin
quantum numbers ms which can take the values of
+½ or –½. These are called the two spin states of
the electron and are normally represented by two
arrows, ↑ (spin up) and ↓ (spin down). An orbital
cannot hold more than two electrons and these
two electrons should have opposite spins.
 Quantum Numbers of Wave functions
Quantum # Symbol Values Description
Principal n 1,2,3,4,… Size & Energy of orbital
Angular l 0,1,2,…(n-1) Shape of orbital
Momentum for each n
Magnetic ml -l…,0,…+ l Relative orientation of
for each l orbitals within same l
Spin ms +1/2 or –1/2 Spin up or Spin down
Angular Momentum Quantum # l Name of Orbital
0 s (sharp)

1 p (principal)
2 d (diffuse)
3 f (fundamental)
4 g
Quantum Mechanics and Atomic Orbitals
Orbitals and Quantum Numbers
 Shapes of Atomic Orbitals
 On plotting ψ2 (electron density) against r (radius),the
following graph was obtained.
 1s 2s

ψ2 ψ2

r r
 On both cases the probability of finding
electron decreases as we move away from the
nucleus. But in 2s, there is an increase in the
electron density and then again decreases. The
region where the probability of finding electron
is zero is called nodes. Nodes can be
calculated using the equation, (n-1)
 Shapes of Orbitals
 Shapes of orbitals are represented by
boundary surface diagrams.
Representations of Orbitals
The s-orbitals
Representations of Orbitals
The p-orbitals
The d-orbitals
 Filling of orbitals in atom
 Aufbau Principle
 The word ‘aufbau’ in German means ‘building up’.
 In the ground state of the atoms, the orbitals are
filled in the increasing order of energies.
 The principle means that electrons first occupy the
lowest energy orbital available to them and enter
into higher energy orbitals only after the lower
energy orbitals are filled.
 Orbitals and Their Energies

Many-Electron Atoms
 The order in which the energies of the orbitals
increase and hence the order in which the
orbitals are filled is as follows :
 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f,5d,
6p, 7s...
 The lower the value of (n + l) for an orbital,
the lower is its energy. If two orbitals have
the same value of (n + l), the orbital with
lower value of n will have the lower energy.
 Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle
 Electron Spin and the
Pauli Exclusion Principle

• Since electron spin is quantized, we define ms =

spin quantum number =  ½.
• Pauli’s Exclusions Principle: no two electrons
can have the same set of 4 quantum numbers.
• Therefore, two electrons in the same orbital must
have opposite spins.
Hund’s Rule of Maximum Multiplicity
 Pairing of electrons in the orbitals belonging to
the same subshell (p, d or f) does not take place
until each orbital belonging to that subshell has
got one electron each i.e., it is singly occupied.
 Stability of Completely Filled and
Half Filled Subshells
 The valence electronic configurations of Cr and Cu
are 3d5 4s1 and 3d10 4s1 respectively and not 3d4 4s2 and
3d9 4s2. It is due to extra stability associated with
completely filled and half filled electronic
configurations. It is due to two major facts
 Symmetry: Due to symmetry, they have extra
stability due to relatively less shielding.
 Exchange Energy: Same spin electrons tend to
exchange their positions and the energy released due
to this exchange is called exchange energy. This large
exchange energy also stabilises the atom.