Session 1

2.2 Atomic models

Why?????....................

• The major problems before the scientists after the discovery of sub-atomic
particles were:
- to account for the stability of atom,
- to compare the behaviour of elements in terms of both physical and
chemical properties,
- to explain the formation of different kinds of molecules by the
combination of different atoms
- to understand the origin and nature of the characteristics of
electromagnetic radiation absorbed or emitted by atoms.
2.2 Atomic Models:
2.2.1 Thomson model of atom:

J. J. Thomson
in 1898
Plum pudding,
Raisin pudding
or
Watermelon model

Important feature:
The mass of the atom is assumed to be uniformly distributed over the atom.
New Rays…………….
• In the later half of the nineteenth century different kinds of rays were
discovered
• Henri Becqueral (1852-1908) observed that there are certain elements which
emit radiation on their own and named this phenomenon as radioactivity and
the elements known as radioactive elements.
• X-rays, α-, β- and γ-rays….
• Rutherford found that
-- α-particles consists of high energy particles carrying two units of
positive charge and four unit of atomic mass. (They are He nucleus).
-- β-rays are negatively charged particles are similar to electrons.
-- γ-rays do not contain particles, but are high energy radiations like X-
rays, are neutral in nature
2.2.2 Rutherford’s Nuclear Model of Atom:
α–particle scattering experiment:
2.2.2 Rutherford’s Nuclear Model of Atom:
• α–particle scattering experiment:
 Results:
• It was expected that: • It was observed that:
The particles would slow down most of the α–particles passed
and change directions only by a small through the gold foil undeflected.
angles as they passed through the a small fraction of the a–particles
foil. was deflected by small angles.
a very few α–particles (~1 in 20,000)
bounced back, that is, were deflected
by nearly 180°.
Rutherford’s conclusions regarding the structure of
atom:
(i) Most of the space in the atom is empty as most of the a–particles passed
through the foil undeflected.
(ii) A few positively charged a–particles were deflected. The deflection must
be due to enormous repulsive force showing that the positive charge of the
atom is not spread throughout the atom as Thomson had presumed. The
positive charge has to be concentrated in a very small volume that repelled
and deflected the positively charged a–particles.
(iii) Calculations by Rutherford showed that the volume occupied by the
nucleus is negligibly small as compared to the total volume of the atom.
The radius of the atom is about 10–10 m, while that of nucleus is 10–15 m.
Rutherford proposed the nuclear model of atom:

(i) The positive charge and most of the mass of the atom was densely
concentrated in extremely small region. This very small portion of the atom was
called nucleus by Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a
very high speed in circular paths called orbits. Thus, Rutherford’s model of
atom resembles the solar system in which the nucleus plays the role of sun and
the electrons that of revolving planets.
(iii) Electrons and the nucleus are held together by electrostatic forces of
attraction.
• https://youtu.be/TbAa9K41PVM
• Rutherfords model of atom
2.2.3 Atomic Number and Mass Number:

Protons and neutrons present in the

nucleus are collectively known as nucleons
2.2.4 Isobars and Isotopes:

Isobars are the atoms with same mass number but different atomic number.

14 14
Eg: 6𝐶, 7𝑁

Isotopes are atoms with identical atomic number but different atomic mass
number.
Eg: , , .

All the isotopes of a given element show same chemical behaviour. Why???
 Reason:
• Chemical properties of atoms are controlled by
- the number of electrons, which are determined by the number
of protons in the nucleus.
- Number of neutrons present in the nucleus have very little
effect on the chemical properties of an element.
Let’s solve……………..
Let’s solve……………..
Drawbacks of Rutherford model:

• Rutherford model cannot explain the stability of an

atom.
• It says nothing about distribution of the electrons
around the nucleus and the energies of these electrons.
 Session 2
2.3 DEVELOPMENTS LEADING TO THE
BOHR’S MODEL OF ATOM
Two main developments……….

(i) Dual character of the electromagnetic radiation

which means that radiations possess both wave like
and particle like properties.
(ii) Experimental results regarding atomic spectra.
 2.3 DEVELOPMENTS LEADING TO THE
BOHR’S MODEL OF ATOM:
2.3.1 Wave Nature of Electromagnetic Radiation
2.3.2 Particle Nature of Electromagnetic Radiation:
Planck’s Quantum Theory
Photoelectric Effect
Dual Behaviour of Electromagnetic Radiation
2.3.3 Evidence for the quantized* Electronic Energy Levels:
Atomic spectra
Emission and Absorption Spectra
Line Spectrum of Hydrogen
2.3.1 Wave Nature of Electromagnetic
Radiation:
• Thermal radiations: Absorption and emission of radiation by heated
objects.
• What the thermal radiation is made of????
• Now we know that…..(unknown in the mid-nineteenth century)
• Thermal radiations consist of electromagnetic waves of various
frequencies or wavelengths.
 Study on electromagnetic radiations…1870….

• 1870 -- James Clerk Maxwell-(the theory of electromagnetic waves and the

emission of such waves by accelerating charged particles was developed)
• Heinrich Hertz –(experimentally confirmed)
Study on electromagnetic radiations…1870….
• 1870 -- James Clerk Maxwell
• He suggested that when electrically charged particle moves under acceleration,
alternating electrical and magnetic fields are produced and transmitted.
• These fields are transmitted in the forms of waves called electromagnetic
waves or electromagnetic radiation.
• Light was supposed to be made of particles (corpuscules).
• In the 19th century wave nature of light was established.
• Maxwell was again the first to reveal that light waves are associated with
oscillating electric and magnetic character
Electromagnetic Radiation:
Some simple properties of Electromagnetic Radiations:

(i) The oscillating electric and magnetic fields produced by oscillating charged particles
are perpendicular to each other and both are perpendicular to the direction of
propagation of the wave.
(ii) Unlike sound waves or waves produced in water, electromagnetic waves do not
require medium and can move in vacuum.
(iii) It is now well established that there are many types of electromagnetic radiations,
which differ from one another in wavelength (or frequency). These constitute what
is called electromagnetic spectrum.
Different regions of the spectrum are identified by different names.
(iv) Different kinds of units are used to represent electromagnetic radiation.
Electromagnetic spectrum:

• .
Electromagnetic Radiation:
• These radiations are characterised by the properties, namely, frequency (ν ) and
wavelength (λ).
• SI unit for frequency (ν ) is hertz (Hz, 𝑠 −1 ).
It is defined as the number of waves that pass a given point in one second.
 Electromagnetic Radiation:
• In vaccum, all types of electromagnetic radiations, regardless of wavelength,
travel at the same speed, i.e., 3.0 × 108 𝑚𝑠 −1 .
• This is called speed of light and is given the symbol ‘c‘.
• The frequency (ν ), wavelength (λ) and velocity of light (c) are related by the
equation.
c=νλ
• In spectroscopy we use another quantity i.e the wavenumber.
• It is defined as the number of wavelengths per unit length.
• Its units are reciprocal of wavelength unit, i.e., 𝑚−1 .
• However commonly used unit is 𝑐𝑚−1
 Session 3
2.3.2
Particle Nature of Electromagnetic
Radiation
 2.3 DEVELOPMENTS LEADING TO THE
BOHR’S MODEL OF ATOM:
2.3.1 Wave Nature of Electromagnetic Radiation
2.3.2 Particle Nature of Electromagnetic Radiation:
Planck’s Quantum Theory
Photoelectric Effect
Dual Behaviour of Electromagnetic Radiation
2.3.3 Evidence for the quantized* Electronic Energy Levels:
Atomic spectra
Emission and Absorption Spectra
Line Spectrum of Hydrogen
Let’s learn about……………..
2.3.2 Particle Nature of Electromagnetic Radiation:
Planck’s Quantum Theory
Photoelectric Effect
Dual Behaviour of Electromagnetic Radiation
Wave Nature Could explain ………………
Diffraction and Interference:
• Diffraction is the bending of wave around an obstacle.
• Interference is the combination of two waves of the same or different
frequencies to give a wave whose distribution at each point in space is
the algebraic or vector sum of disturbances at that point resulting
from each interfering wave.
Wave Nature Couldn’t explain ………………
Photoelectric effect
2.3.2 Particle Nature of Electromagnetic Radiation:
• The following are some of the observations which could not be explained with the
help of even the electromagentic theory of 19th century physics (known as
classical physics):
(i) the nature of emission of radiation from hot bodies (black -body radiation)
(ii) ejection of electrons from metal surface when radiation strikes it
(photoelectric effect)
(iii) variation of heat capacity of solids as function of temperature.
(iv) Line spectra of atoms with special reference to hydrogen.

• These phenomena indicate that the system can take energy only in discrete
amounts.
2.3.2 Particle Nature of Electromagnetic Radiation:

• Black Body Radiation:

2.3.2 Particle Nature of Electromagnetic Radiation:
• Explanation for the phenomenon of the black body
radiation was first given by Max Planck in 1900.
• Hot objects emit electromagnetic radiations over a wide
range of wavelengths. At high temperatures, an appreciable
proportion of radiation is in the visible region of the spectrum. As the
temperature is raised, a higher proportion of short wavelength (blue light) is
generated.
2.3.2 Particle Nature of Electromagnetic Radiation:
Black Body Radiation:
• An ideal body, which emits and absorbs radiations of all frequencies uniformly,
is called a black body
• The radiation emitted by such a body is called black body radiation.
• In practice, no such body exists.
• Carbon black approximates fairly closely to black body.
• Carbon black is a material produced by the incomplete combustion of heavy
petroleum products such as FCC(Fluid catalytic cracking) tar, coal tar, or
ethylene cracking tar. It is a form of paracrystalline carbon that has a high
surface-area-to-volume ratio.
2.3.2 Particle Nature of Electromagnetic Radiation:
Black Body Radiation:
• A black body is in thermal equilibrium with its
surroundings.
• It radiates same amount of energy per unit
area as it absorbs from its surrounding in
any given time.
• The amount of light emitted (intensity of
radiation) from a black body and its spectral
distribution depends only on its temperature.
2.3.2 Particle Nature of Electromagnetic Radiation:
Black Body Radiation:
• At a given temperature, intensity of radiation
emitted increases with the increase of
wavelength, reaches a maximum value at a
given wavelength and then starts decreasing
with further increase of wavelength.
• Also, as the temperature increases,
maxima of the curve shifts to short wavelength.
2.3.2 Particle Nature of Electromagnetic Radiation:

Black Body Radiation:

• Several attempts were made to predict the intensity of radiation as a
function of wavelength.
2.3.2 Particle Nature of Electromagnetic Radiation:
Black Body Radiation:
• Max Planck arrived at a satisfactory relationship by making the following assumptions:
- Absorption and emmission of radiation arises from oscillator i.e., atoms
in the wall of black body.
- Their frequency of oscillation is changed by interaction with oscilators of
electromagnetic radiation.
- Radiation could be sub-divided into discrete chunks of energy.
• He suggested that atoms and molecules could emit or absorb energy only in discrete
quantities and not in a continuous manner.
• He gave the name quantum to the smallest quantity of energy that can be emitted or
absorbed in the form of electromagnetic radiation.
• The energy (E ) of a quantum of radiation is proportional to its frequency (ν )
𝑬 = 𝒉𝝂
• The proportionality constant, ‘h’ is known as Planck’s constant and has the value
6.626 × 10−34 𝐽𝑠.
2.3.2 Particle Nature of Electromagnetic Radiation:
Black Body Radiation:
• 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.
• The energy can take any one of the values from
the following set, but cannot take on any values
between them.
E = 0, hu, 2hu, 3hu....nhu.....
2.3.2 Particle Nature of Electromagnetic Radiation:

• Photoelectric effect:
2.3.2 Particle Nature of Electromagnetic Radiation:
Photoelectric effect:
• In 1887, H. Hertz performed a very interesting 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.
2.3.2 Particle Nature of Electromagnetic Radiation:
Photoelectric effect:
• The results observed in this experiment were:
Photoelectric effect:

All the above results could not be explained

on the basis of laws of classical physics.
Photoelectric effect:
• According to classical physics, the energy
content of the beam of light depends upon
the brightness of the light.
OR
The number of electrons ejected and kinetic energy
associated with them should depend on the
brightness of light.
• It has been observed that
- the number of electrons ejected does depend upon the brightness
of light.
- the kinetic energy of the ejected electrons does not.
Photoelectric effect:
• Eg: red light [ν = (4.3 to 4.6) × 𝟏𝟎𝟏𝟒 Hz] of any brightness (intensity)
may shine on a piece of potassium metal for hours but no
photoelectrons are ejected.
• a very weak yellow light (ν = 5.1–5.2 × 𝟏𝟎𝟏𝟒 Hz) shines on the
potassium metal, the photoelectric effect is observed.
• The threshold frequency (ν0 ) for potassium metal is 5.0×𝟏𝟎𝟏𝟒 Hz.
Photoelectric effect:
• Einstein (1905) was able to explain the photoelectric effect using
Planck’s quantum theory of electromagnetic radiation.
• Greater the energy possessed by the photon,
greater will be transfer of energy to the electron
greater the kinetic energy of the ejected electron.
• K.E ∝ frequency
of the ejected of the electromagnetic
electron. radiation.
Photoelectric effect:

• Energy of the striking photon = ℎν

• The minimum energy required to eject
the electron(work function;𝑾𝟎 ) = 𝒉𝝂𝟎
• The difference in energy = ℎν − ℎν0
• This energy is transferred as the kinetic energy
of the photoelectron.
• Following the conservation of energy principle,
the kinetic energy of the ejected electron
is given by OR 𝑾𝟎 = ℎν -
Dual Behaviour of Electromagnetic Radiation:
Let’s solve some problems………….

.
 Session: 5
2.3.3
Evidence for the quantized Electronic Energy Levels:
Atomic spectra
Emission and Absorption Spectra
Spectrum:
• The speed of light depends upon the nature of the medium through which it passes.
• As a result, the beam of light is deviated or refracted from its original path as it
passes from one medium to another.
• When a ray of white light is passed through a prism, the wave with shorter
wavelength bends more than the one with a longer wavelength.
• Frequency:
Violet -- 7.50 ×1014 𝐻𝑧 Red -- 4×1014 𝐻𝑧
deviated the most deviated the least
• Since 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.
Continuous spectrum:
• In the spectrum produced by visible light, Violet merges into blue,
blue into green and so on. Such a spectrum is called continuous
spectrum.
• Visible light is just a small portion of the electromagnetic radiation.
• When electromagnetic radiation interacts with matter, atoms and
molecules may absorb energy and reach to a higher energy state.
• With higher energy, these are in an unstable state.
• For returning to their normal (more stable, lower energy states)
energy state, the atoms and molecules emit radiations in various
regions of the electromagnetic spectrum.
Emission and Absorption Spectra:
Emission spectrum:
The spectrum of radiation emitted by a substance that has absorbed
energy is called an emission spectrum.
• Atoms, molecules or ions that have absorbed radiation are said to be “excited”.
• To produce an emission spectrum, energy is supplied to a sample
- by heating it or irradiating it
• And the wavelength (or frequency) of the radiation emitted, as the sample gives up
the absorbed energy, is recorded.
Absorption spectrum:
A continuum of radiation is passed through a sample which absorbs
radiation of certain wavelengths.
• The missing wavelength which corresponds to the radiation absorbed by the matter,
leave dark spaces in the bright continuous spectrum. This is called absorption
spectrum.
Spectroscopy:
• The study of emission or absorption spectra is referred to as spectroscopy.
• The spectrum of the visible light, is continuous as all wavelengths (red to
violet) of the visible light are represented in the spectra.
• The emission spectra of atoms in the gas phase, on the other hand, do not
show a continuous spread of wavelength from red to violet, rather they
emit light only at specific wavelengths with dark spaces between them.
• Such spectra are called line spectra or atomic spectra
- because the emitted radiation is identified by the appearance of
bright lines in the spectra.
• Each element has a unique line emission spectrum.
(a) Atomic emission:
The light emitted by a sample of excited hydrogen atoms (or any other element) can be
passed through a prism and separated into certain discrete wavelengths.
Thus an emission spectrum, which is a photographic recording of the separated
wavelengths is called as line spectrum.
Any sample of reasonable size contains an enormous number of atoms.
Although a single atom can be in only one excited state at a time, the collection of atoms
contains all possible excited states. The light emitted as these atoms fall to lower energy states
is responsible for the spectrum.
(b) Atomic absorption:
When white light is passed through unexcited atomic hydrogen and then
through a slit and prism, the transmitted light is lacking in intensity at the same
wavelengths as are emitted in (a)
The recorded absorption spectrum is also a line spectrum and the
photographic negative of the emission spectrum.
Continuous, Absorption, Emission Spectra:

.
Line emission spectrum or Atomic Spectrum:
• The characteristic lines in atomic spectra can be used
- in chemical analysis to identify unknown atoms. (fingerprints)
• The exact matching of lines of the emission spectrum of the atoms of a known
element with the lines from an unknown sample quickly establishes the
identity of the latter.
• German chemist, Robert Bunsen (1811-1899) was one of the first investigators
to use line spectra to identify elements.
• Elements like rubidium (Rb), caesium (Cs), thallium (Tl), indium (In), gallium
(Ga) and scandium (Sc) were discovered when their minerals were analysed by
spectroscopic methods.
• The element helium (He) was discovered in the sun by spectroscopic method.
Spectrum for different elements:
Line Spectrum of Hydrogen:
• When an electric discharge is passed through gaseous hydrogen, the H2
molecules dissociate.
• The energetically excited hydrogen atoms produced emit electromagnetic
radiation of discrete frequencies.
• The hydrogen spectrum consists of several series of lines named after their
discoverers.
• Balmer showed in 1885 on the basis of experimental observations that if
spectral lines are expressed in terms of wavenumber (ν), then the visible lines
of the hydrogen spectrum obey the following formula:

where n is an integer equal to or greater than 3 (i.e., n = 3,4,5,....)

• The series of lines described by this formula are called the Balmer series.
Line Spectrum of Hydrogen:

• General expression for all series of lines in the hydrogen spectrum

- By the Swedish spectroscopist, Johannes Rydberg.

• The value 𝟏𝟎𝟗, 𝟔𝟕𝟕𝒄𝒎−𝟏 is called the Rydberg constant for hydrogen.
Line Spectrum of Hydrogen:

Values of 𝒏𝟏 &𝒏𝟐
Line Spectrum of Hydrogen:
Line Spectrum of Hydrogen:

• Features which are common to all line spectra are

(i) line spectrum of element is unique and
(ii) there is regularity in the line spectrum of each element.
• The questions which arise are:
- What are the reasons for these similarities?
- Is it something to do with the electronic structure of atoms?
 Session: 6
2.4
BOHR’S MODEL FOR HYDROGEN ATOM
BOHR’S MODEL FOR HYDROGEN ATOM:
• Neils Bohr (1913) was the first to explain
quantitatively the general features of the
structure of hydrogen atom and its spectrum.
• He used Planck’s concept of quantisation of energy.
• The theory is not the modern quantum mechanics.
BOHR’S MODEL FOR HYDROGEN ATOM:
Bohr’s model for hydrogen atom is based on the following postulates:
i)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.
ii) 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 by the electron or
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.
BOHR’S MODEL FOR HYDROGEN ATOM:
iii) The frequency of radiation absorbed or emitted when transition occurs
between two stationary states that differ in energy by ∆𝐸, is given by:

(Where E1 and E2 are the energies of the lower and higher allowed
energy states respectively)
• This expression is commonly known as Bohr’s frequency rule.
BOHR’S MODEL FOR HYDROGEN ATOM:
iv) The angular momentum of an electron is quantised.
In a given stationary state it can be expressed as in
equation:

where n = 1,2,3.....,
𝑚𝑒 is the mass of electron,
v is the velocity and
r is the radius of the orbit in which electron is moving.
BOHR’S MODEL FOR HYDROGEN ATOM:

• Thus an electron can move only in those orbits for which its angular momentum
ℎ
is integral multiple of .
2𝜋
• Radiation is emitted or absorbed only when transition of electron takes place
from one quantised value of angular momentum to another.
• That is why only certain fixed orbits are allowed.
BOHR’S MODEL FOR HYDROGEN ATOM:
Bohr’s theory for hydrogen atom:
a) The stationary states for electron are numbered n = 1,2,3..........
These integral numbers are known as Principal quantum numbers.
b) The radii of the stationary states are expressed as:
where 𝑎0 = 52.9 pm.
Thus the radius of the first stationary state, called the Bohr orbit, is 52.9 pm.
Normally the electron in the hydrogen atom is found in this orbit (that is n=1).
c) The most important property associated with the electron, is the energy of its
stationary state, given by the expression:
BOHR’S MODEL FOR HYDROGEN ATOM:

• where 𝑅𝐻 is called Rydberg constant and its

value is 2.18 × 10−18 𝐽
• The energy of the lowest state, also called as the ground state, is

• The energy of the stationary state for n = 2, will be :

BOHR’S MODEL FOR HYDROGEN ATOM:
• Energy level diagram of Hydrogen atom:
• When the electron is free from the influence
of nucleus, the energy is taken as zero.
• The electron in this situation is associated with
the stationary state of Principal Quantum number
𝑛 = ∞ and is called as ionized hydrogen atom.
• When the electron is attracted by the nucleus
and is present in orbit n, the energy is emitted
and its energy is lowered.
• That is the reason for the presence of negative sign
and depicts its stability relative to the reference state
of zero energy and 𝑛 = ∞
BOHR’S MODEL FOR HYDROGEN ATOM:
d) Bohr’s theory can also be applied to the ions containing only one electron,
similar to that present in hydrogen atom.
Eg: He+ Li2+, Be3+ and so on.
The energies of the stationary states associated with these kinds of ions (also
known as hydrogen like species) are given by thexpression:

and radii by the expression:

where Z is the atomic number and Z = 2 for helium and Z = 3 for lithium atom.
BOHR’S MODEL FOR HYDROGEN ATOM:

• From these equations, it is evident that

the value of energy becomes more negative and
that of radius becomes smaller with increase of Z .
• This means that electron will be tightly bound to
the nucleus.
BOHR’S MODEL FOR HYDROGEN ATOM:
e) It is also possible to calculate the velocities of electrons moving in these orbits.
• Qualitatively the magnitude of velocity of electron
increases with increase of positive charge on the nucleus and
decreases with increase of principal quantum number.
2.4.1 Explanation of Line Spectrum of Hydrogen
• According to assumption 2,
- radiation (energy) is absorbed if the electron moves from the orbit of
smaller Principal quantum number to the orbit of higher Principal
quantum number,
- radiation (energy) is emitted if the electron moves from higher orbit to
lower orbit.
• The energy gap between the two orbits is given by equation:
But we know that:

Therefore: OR
2.4.1 Explanation of Line Spectrum of Hydrogen

• The frequency (𝝂) associated with the

absorption and emission of the photon:

Wave number (ν):

2.4.1 Explanation of Line Spectrum of Hydrogen

• In case of absorption spectrum, 𝑛𝑓 > 𝑛𝑖 and

the term in the parenthesis is positive and
energy is absorbed.
• In case of emission spectrum 𝑛𝑖 > 𝑛𝑓 , ∆𝐸 is
negative and energy is released.
2.4.1 Explanation of Line Spectrum of Hydrogen

• The expression: is similar to

• Rydberg’s expression:

• Each spectral line, whether in absorption or emission spectrum, can be

associated to the particular transition in hydrogen atom.
• In case of large number of hydrogen atoms, different possible transitions can be
observed and thus leading to large number of spectral lines.
• The brightness or intensity of spectral lines depends upon the number of
photons of same wavelength or frequency absorbed or emitted.
2.4.2 LiMiTATiONS OF BOHR’S Model:
• Bohr’s model of the hydrogen atom was an improvement over Rutherford’s nuclear
model, as it could account for
- the stability and line spectra of hydrogen atom and hydrogen like ions.
• However, Bohr’s model was too simple to account for the following points:
i) It fails to account for the finer details (doublet, that is two closely spaced lines) of
the hydrogen atom spectrum observed by using sophisticated spectroscopic
techniques.
- This model is also unable to explain the spectrum of atoms other than hydrogen,
for example, helium atom which possesses only two electrons.
- Further, 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).
ii) It could not explain the ability of atoms to form molecules by chemical bonds.
2.4.2 LiMiTATiONS OF BOHR’S Model:

• Zeeman effect: • Stark effect:

 Session: 7
2.5
TOWARDS QUANTUM MECHANICAL
MODEL OF THE ATOM
TOWARDS QUANTUM MECHANICAL MODEL OF THE ATOM:

Two important developments which contributed

significantly in the formulation of Quantum Mechanical
model were :

1. Dual behavior of matter,

2. Heisenberg uncertainty principle.
 2.5.1 Dual Behaviour of Matter

• De Broglie, in 1924 proposed that

- matter also exhibit dual behavior
i.e., both particle and wave like properties.
• This means that
- as the photon has momentum as well as wavelength,
Louis de Broglie
electrons should also have momentum as well as wavelength. (1892 – 1987)

• From this analogy, he gave the following relation between

- wavelength (l) and momentum (p) of a material particle.
where m is the mass of the particle,
v its velocity and
p its momentum.
 electron microscope

• based on the wavelike behaviour of electrons

• it achieves a magnification of about 15 million times.
 DE BROGLiE’S EquATiON

• According to de Broglie, every object in motion has a

wave character.
• Large mass --- Short wavelength
--- Wave properties cannot be detected.
• Very small mass --- Long wavelength
--- Can be detected experimentally.
(Refer to Eg:2.12, 2.13, 2.14)
2.5.2 HEiSENBERG’S uNcERTAiNTY Principle:

• A consequence of dual behaviour of matter and radiation.

• It states that,
it is impossible to determine simultaneously, the exact position and
exact momentum (or velocity) of an electron.
• Mathematically,
where ∆𝑥 is the uncertainty in position
∆𝑝𝑥 (or ∆𝑣𝑥 ) is the uncertainty in momentum
(or velocity) of the particle.
 Significance of Uncertainty Principle

• It rules out existence of definite paths or trajectories of

electrons and other similar particles.
• The effect of Heisenberg Uncertainty Principle is significant
only for motion of microscopic objects and is negligible for
that of macroscopic objects.
• In dealing with milligram-sized or heavier objects, the
associated uncertainties are hardly of any real consequence.
 FOR ExAMpLE…………..
FOR AN ELEcTRON……………………………..

• For an electron whose mass is 9.11×10–31 kg., according to

Heisenberg uncertainty principle:
If the uncertainity in position of
an electron is ∆𝑥 = 10−8 𝑚

∆𝒗 =
 FOR ExAMpLE…………..
FOR AN ELEcTRON……………………………..

• It, therefore, means that

- the precise statements of the position and momentum
of electrons have to be replaced by the statements of
probability, that the electron has at a given position and
momentum.
• This is what happens in the quantum mechanical model of
atom.
 Reasons for the Failure of the Bohr Model

• Bohr model of the hydrogen atom,

- not only ignores dual behaviour of matter
- but also contradicts Heisenberg uncertainty principle.
 Session 8
2.6
QUANTUM MECHANICAL MODEL OF
ATOM
Quantum mechanics:

Classical mechanics: Quantum mechanics:

• based on Newton’s laws of motion. • The branch of science that takes into
account the dual behaviour of matter is
• successfully describes the motion of called quantum mechanics.
all macroscopic objects. • It is a theoretical science that deals with the
• which have particle-like behaviour. study of the motions of the microscopic
objects that have both observable wave like
• fails when applied to microscopic and particle like properties.
objects.
• It specifies the laws of motion that these
• Because it ignores the concept of objects obey.
dual behaviour of matter for sub- • When quantum mechanics is applied to
atomic particles and the uncertainty macroscopic objects the results are the
principle. same as those from the classical mechanics.
Quantum mechanics:
• Quantum mechanics was developed independently in 1926 by
- Werner Heisenberg and Erwin Schrödinger.
• The fundamental equation of quantum mechanics was developed by Schrödinger and
it won him the Nobel Prize in Physics in 1933.

- a mathematical operator called Hamiltonian. - wave function(s)

Hydrogen Atom and the Schrödinger Equation:
• When Schrödinger equation is solved for hydrogen atom, the solution gives the
possible energy levels the electron can occupy and the corresponding wave
function(s) (Ψ) of the electron associated with each energy level.
• These quantized energy states and corresponding wave functions which are
characterized by a set of three quantum numbers (principal quantum number
(n), azimuthal quantum number (l) and magnetic quantum number( 𝑚𝑙 ) ) arise
as a natural consequence in the solution of the Schrödinger equation.
• When an electron is in any energy state, the wave function corresponding to
that energy state contains all information about the electron.
• The wave function is a mathematical function whose value depends upon the
coordinates of the electron in the atom and does not carry any physical
meaning.
Hydrogen Atom and the Schrödinger Equation:
• Such wave functions of hydrogen or hydrogen like species with one electron are
called atomic orbitals.
• Such wave functions pertaining to one-electron species are called one-electron
systems.

• The probability of finding an electron to the|Ψ|2 at that point

at a point within an atom ∝

• This results of the hydrogen atom successfully predict all aspects of the
hydrogen atom spectrum.
Important Features of the Quantum Mechanical Model of Atom:
1. The energy of electrons in atoms is quantized (i.e., can only have certain
specific values), for example when electrons are bound to the nucleus
inatoms.
2. The existence of quantized electronic energy levels is a direct result of the
wave like properties of electrons and are allowed solutions of Schrödinger
wave equation.
3. Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously (Heisenberguncertainty principle).
The path of an electron in an atom therefore, can never be determined or
known accurately.
Important Features of the Quantum Mechanical Model of Atom:
4. An atomic orbital is the wave function Ψ for an electron in an atom.
These “one electron orbital wave functions” or orbitals form the basis of the
electronic structure of atoms.
In each orbital, the electron has a definite energy.
An orbital cannot contain more than two electrons.
In a multi-electron atom, the electrons are filled in various orbitals in the order
of increasing energy.
5. The probability of finding an electron at a point within an atom is proportional
to the square of the orbital wave function i.e., |Ψ|2 at that point.
|Ψ|2 is known as probability density and is always positive.
2.6.1 Orbitals and Quantum Numbers:
• Atomic orbitals are precisely distinguished by quantum numbers.
• Each orbital is designated by three quantum numbers labelled as
n - Principal Quantum number - Energy level or Shell(values of n = 1,2,3.......)
l - Azimuthal Quantum number, orbital angular momentum or
subsidiary quantum number - 3D-Shape of the orbital (0 to n – 1 values)
𝒎𝒍 - Magnetic Quantum number - Spatial orientation w.r.t standard set of co-
ordinate axis. (2l+1 values of 𝑚𝑙 for each l )
𝒎𝒔 - Spin Quantum Number -
• Number of sub-shells in a principal shell is equal to the value of n.
• Each sub-shell is assigned an azimuthal quantum number (l).
Principal Quantum Number:
• The Principal Quantum Number(n) defines the shell, determines
- the size of the orbital
- the energy of the orbital.
• Values of n = 1,2,3.......
• There are n sub shells in the nth shell.
• I.e The 1st shell contains 1 sub shell, i.e only ‘s’
2nd shell contains 2 i.e ‘s’ and ‘p’ and so on……
• The number of allowed orbitals = ‘𝑛2 ’ (In a particular shell)
• i.e 1st shell: n = 1, No. of orbitals = 𝑛2
= 12 = 1 (1s)
2nd shell: n = 2, No. of orbitals = 𝑛2
= 22 = 4 (1s and 3p)
3rd shell: n = 3, No. of orbitals = 𝑛2
= 32 = 9 (1s and 3p and 5d)
Azimuthal Quantum Number:
• The Azimuthal Quantum Number (l) identifies the subshell.
• It determines the shape of the orbital.
• No. of orbitals in a sub shell = (2l+1) orbitals.
• For eg: one s orbital (l = 0),
three p orbitals (l = 1) and
five d orbitals (l = 2) per subshell.
• To some extent l also determines the energy
of the orbital in a multi-electron atom.
Magnetic quantum number:
• Magnetic Quantum Number(𝑚𝑙 ) designates the orientation of the orbital.
• For a given value of l, 𝑚𝑙 has (2l+1) values.
• It is the same as the number of orbitals per subshell.
• It means that the number of orbitals is equal to the number of ways in which they are
oriented.
No. of Orbitals
Shell orbitals
(n) (𝒏𝟐 )
1 1 1s
2 4 One 2s
Three 2p
3 9 One 3s
Three 3p
Five 3d
Spin quantum number:
• In 1925, George Uhlenbeck and Samuel Goudsmit proposed the presence of the
fourth quantum number known as the electron spin quantum number (𝒎𝒔 ).
• Spin angular momentum of the electron — a vector quantity, can have two
orientations relative to the chosen axis.
• These two orientations are distinguished by the spin quantum numbers 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).
• Two electrons that have different 𝒎𝒔 values (one +½ and the other –½) are said to
have opposite spins.
• An orbital cannot hold more than two electrons and these two electrons should have
opposite spins.
• 𝒎𝒔 refers to orientation of the spin of the electron.
Orbitals and Quantum Numbers:
Quantum numbers:
• Summary:
Quantum numbers:
• Summary:
LET’S SOLvE………….
• Q: 1
LET’S SOLvE………….
• Solution:1
LET’S SOLvE………….
• Q: 2
LET’S SOLvE………….
• Solution:2
 Session 9
2.6.2 Shapes of Atomic Orbitals
2.6.3 Energies of Orbitals
s – Orbital:
(a) the orbital wave function Ψ(r );
(b) the variation of probability density Ψ 2 (r)
as a function of distance r of the electron
from the nucleus for 1s and 2s orbitals.
• For 1s orbital the probability density is maximum
at the nucleus and it decreases sharply as we
move away from it.
• For 2s orbital the probability density first
decreases sharply to zero and again starts
increasing.
After reaching a small maxima it decreases again
and approaches zero as the value of r increases further.
s – Orbital:

Charge cloud diagram Boundary Surface diagram

The size of the s orbital increases with

increase in n, It encloses a region in which probability
i.e, 4s > 3s > 2s > 1s
of finding the electron is about 90%.
p – Orbital:
Boundary Surface diagram:
- The size, shape and energy of the
three orbitals are identical.
- The order of the energy and size of
p orbitals increases with n,
i.e 4p > 3p > 2p.
d – Orbital:
Boundary Surface diagram:

- all five 3d orbitals are equivalent in energy.

Nodes:
• The region where the probability
density function reduces to zero is called
nodal surfaces or simply nodes.
• ns-orbital has (n – 1) nodes.
• Number of nodes increases with increase
of principal quantum number n.
OR
Number of nodes for 1s orbital is zero
2s orbital is one,
3s orbital is two and so on.
Nodes:
• Besides the radial nodes (i.e., probability density function is zero), the
probability density functions for the np and nd orbitals are zero at the plane (s),
passing through the nucleus (origin).
• For example, in case of pz orbital, xy-plane is a nodal plane, in case of dxy
orbital, there are two nodal planes passing through the origin and bisecting the
xy plane containing z-axis. These are called angular nodes.
• The number of angular nodes are given by ‘l’, i.e., one angular node for p
orbitals, two angular nodes for ‘d’ orbitals and so on.
• The total number of nodes = No. of angular nodes + No. of radial nodes
= l + (n – l – 1)
= n–1
Nodes:
2.6.3 Energies of Orbitals: In H and H-like species…
• The energy of an electron in a hydrogen atom is
determined solely by the principal quantum number.
• The energy of the orbitals in hydrogen atom increases
as follows :
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d= 4f <
• The orbitals having the same energy are called degenerate.
- The only electrical interaction present in hydrogen atom
is the attraction between the negatively charged electron and the
positively charged nucleus.
• The 1s orbital in a hydrogen atom, corresponds to the most
stable condition and is called the ground state.
• An electron residing in this orbital is most strongly held by
the nucleus.
• An electron in the 2s, 2p or higher orbitals in a hydrogen
atom is in excited state.
2.6.3 Energies of Orbitals: In multielectron atoms….
• The energy of an electron in a multi electron atom, depends
- on its principal quantum number (shell),
- on its azimuthal quantum number (subshell).
• Within a given principal quantum number, the energy
of orbitals increases in the order s<p<d<f.
• For higher energy levels, these differences are sufficiently
pronounced and straggering of orbital energy may result,
e.g., 4s<3d and 6s<5d ; 4f<6p.
• The main reason for having different energies of the
subshells is the mutual repulsion among the electrons in
multielectron atoms.
2.6.3 Energies of Orbitals: In multielectron atoms….
Attractions & Repulsions: Diagram:

• In multielectron atoms, there exists .

- attraction between the electron
and nucleus.
- repulsion between every electron
and other electrons present in the
atom.
• Thus the stability of an electron in a
multi-electron atom is because
Total attractive interactions > The
repulsive interactions
2.6.3 Energies of Orbitals: In multielectron atoms….
Shielding effect &Effective Nuclear charge: Diagram:
• Due to the presence of electrons in the .
inner shells, the electron in the outer
shell will not experience the full positive
charge of the nucleus (Ze).
• The effect will be lowered due to the
partial screening of positive charge on
the nucleus by the inner shell electrons.
This is known as the shielding of the
outer shell electrons from the nucleus
by the inner shell electrons, and the net
positive charge experienced by the outer
electrons is known as effective nuclear
charge (Zeff e).
• Both the attractive and repulsive interactions depend
upon the shell and shape of the orbital in which the
electron is present.
• Shielding effect:
𝑠 − 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 > 𝑝 − 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 > 𝑑 − 𝑜𝑟𝑏𝑖𝑡𝑎𝑙 > 𝑓 − 𝑜𝑟𝑏𝑖𝑡𝑎𝑙
• For a given shell (principal quantum number), the 𝒁𝒆𝒇𝒇 experienced by the
electron decreases with increase of azimuthal quantum number (l).
• That is, the s orbital electron will be more tightly bound to the nucleus than p
orbital electron which in turn will be better tightly bound than the d orbital
electron.
• Therefore the energy of electrons in various orbitals will follow the order:
𝑠<𝑝<𝑑<𝑓
 Diagram:

Effect of shielding:
.
• Since the extent of shielding from the nucleus
is different for electrons in different orbitals, it
leads to the splitting of energy levels within the
same shell.
OR
Energy of electron in an orbital, depends upon
the values of n and l.
• Mathematically,
- 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.
2.6.3 Energies of Orbitals: In multielectron atoms….
.
Energies of the orbitals in the same subshell decrease with increase
in the atomic number (Zeff).

For example,
Energy of 2s orbital of hydrogen atom is greater than that of 2s
orbital of lithium and that of lithium is greater than that of sodium and so
on,

That is, E2s(H) > E2s(Li) > E2s(Na) > E2s(K).

 Session 10

2.6.4 Filling of Orbitals in Atom

Filling of electrons into the orbitals:
• The filling of electrons into the orbitals of different atoms takes place according
to
The aufbau principle,
which is based on
*The Pauli’s exclusion principle
*The Hund’s rule of maximum multiplicity and
*The relative energies of the orbitals.
Aufbau Principle:
‘aufbau’ - a German word
- means ‘building up’.

In the ground state of the atoms, the

orbitals are filled in order of their increasing
energies.
OR
Electrons first occupy the lowest energy
orbital available to them and enter into higher
energy orbitals only after the lower energy
orbitals are filled.
Aufbau Principle:

The order of filling orbitals =>

So the order is
1s, 2s, 2p, 3s, 3p, 4s,
3d, 4p, 5s, 4d, 5p, 6s…..
Pauli Exclusion Principle:

“No two electrons in an atom can have the same set

of four quantum numbers”.
OR
“Only two electrons may exist in the same orbital and
these electrons must have opposite spin.”

So The maximum number of electrons in the

shell with principal quantum number ‘n’ = 2𝑛2
Hund’s Rule of Maximum Multiplicity:

It states :
“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”.

• The pairing of electrons will start in the p, d and f orbitals with the entry of
4th, 6th and 8th electron, respectively.
• It has been observed that half filled and fully filled degenerate set of orbitals
acquire extra stability due to their symmetry.
 Session: 11
2.6.5 Electronic Configuration of Atoms
2.6.6 Stability of Completely Filled and
Half Filled Subshells
 2.6.5 Electronic Configuration of Atoms:
• The distribution of electrons into orbitals of an atom is called its electronic
configuration.
• The electronic configuration of different atoms can be represented in two ways.
For ex:

1s 2s 2p 3s
↑
Na - 1𝑠 2 2𝑠 2 2𝑝6 3𝑠1 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

• The advantage of second notation over the first is that it represents all the four
quantum numbers.
Core electrons and Valence electrons:
Core electrons:
• The electrons in the completely filled shells are known as core electrons.
Valence electrons:
• The electrons that are added to the electronic shell with the highest principal
quantum number are called valence electrons.

Na – ( 1𝑠 2 2𝑠 2 2𝑝6 ) 3𝑠1
Core electrons Valence electron
Electronic Configuration of first 18 elements:
.
Exemptions:
.
Electronic Configuration and Periodic Table:
.
Periodic Table of elements:
.
What is the utility of knowing the electron configuration?
• To understand and explain chemical behavior of elements.
For example: We can find simple explanation for the following questions
from the electronic configuration of elements.
• Why two or more atoms combine to form molecules?
• Why some elements are metals while others are nonmetals?
• Why elements like helium and argon are not reactive but elements like the
halogens are reactive?
These questions have no answer in the Daltonian model of atom.
2.6.6 Stability of Completely Filled and
Half Filled Subshells:
• The ground state electronic configuration of the atom of an element
- state of the lowest total electronic energy.
Causes of Stability of Completely Filled and Half-filled Subshells:

• The completely filled and completely half-filled subshells are stable due to the
following reasons:
1. Symmetrical distribution of electrons:
- symmetry leads to stability.
- Electrons in the same subshell (here 3d) have equal energy but different
spatial distribution.
- Consequently, their shielding of one another is relatively small and the
electrons are more strongly attracted by the nucleus.
Causes of Stability of Completely Filled and Half-filled Subshells:

2. Exchange Energy :
- The stabilizing effect arises whenever two or more electrons with the
same spin are present in the degenerate orbitals of a subshell.
- These electrons tend to exchange their positions and the energy released
due to this exchange is called exchange energy.
- The number of exchanges that can take place is maximum when the
subshell is either half filled or completely filled.
- As a result the exchange energy is maximum and so is the stability.
Causes of Stability of Completely Filled and Half-filled Subshells:
2. Exchange Energy : for a d-orbital, 10 exchanges are possible
Causes of Stability of Completely Filled and Half-filled Subshells:
• In other words, the extra stability of half-filled and completely filled subshell is
due to:
(i) relatively small shielding,
(ii) smaller coulombic repulsion energy, and
(iii) larger exchange energy.
THANK YOU !!!