ATOMIC STRUCTURE

Course Outlines
• Atom structure and limitations of Bohr's
model
• Wave particle duality, De Broglie's principle
and numerical problems based on it
• Schrödinger's wave equation (no derivation).
Atomic orbital, shapes of s, p, d, f orbitals
• Electronic configuration of atoms and Concept
of hybridization (sp, sp2, sp3) with one
example each
 Atomic Structure
All matter is composed of atoms.
Understanding the structure of atoms is critical
to understanding the properties of matter

"An atom is an indivisible

particle and is the building
block of all matter present".

400 BC Democritus
 Dalton's atomic theory

Wrote the first atomic theory

John Dalton
(1766 – 1844)
1. All elements are composed of tiny indivisible particles called
atoms
2. Atoms of the same element are identical. Atoms of any one
element are different from those of any other element.
3. Atoms of different elements combine in simple whole-number
ratios to form chemical compounds
4. In chemical reactions, atoms are combined, separated, or
rearranged – but never changed into atoms of another element.
 Daltons atomic theory

16 X + 8Y 8 X2Y
 Discovery of Electron
Michael Faraday (1830) showed that if electricity is passed through a
solution of an electrolyte, chemical reactions occur at electrodes,
which resulted in liberation and deposition of matter at electrodes.
In mid 1890s many scientists mainly J.J. Thomson begun to study
electrical discharge in partially evacuated tube, known as cathode
rays discharge tubes (Figure).

Joseph John Thompson

 Cathode rays experiment’s results
 Cathode rays start from cathode and moved towards the anode
 These rays are not visible, but when falling on fluorescent/
phosphorescent material it glows
 In absence of electrical or magnetic field these rays travel
straight lines
 In the presence of electrical or magnetic field cathode rays get
deflected towards positive side and behavior observed like
negatively charged particles, called as electrons
 The characteristic of cathode rays do not depend upon the
material of electrodes and nature of gas present in cathode rays
tube.
Thus, we can conclude that electrons are basic constituents of all
atoms.
 J. J. Thomson measured the charge-by-mass-ratio (e/m) of cathode
ray particle using deflection in both electric and magnetic field.
A = alpha
B = gamma
e/m=−1.76×108 coulomb per gram
C = beta The cathode ray particle turned out to be 2000 times lighter than
hydrogen.
J . J. Thompson Plum pudding model
• J.J. Thomson discovered the electron and knew that electrons
could be emitted from matter (1897).
• William Thomson proposed that atoms consist of small,
negative electrons embedded in a massive, positive sphere.
• The electrons were like currants in a plum pudding.
• This is called the ‘plum pudding’ model of the atom.

Thompson's model did not have any

nucleus in it and first time experimentally
something was proposed.
Robert A. Millikan

 He measured the charge of electrons in his oil

drop experiment in 1909.
 They balanced the gravitational and electric
forces of tiny, charged droplets of oil
suspended between 2 electrodes.
 Knowing the electric field, the charge on the
oil droplet could be determined.
 After repeating the experiment, they found
that the values measured were always
multiples of the same number.
 They found the charge of a single electron to
be 1.602x10-19C.
10
 Millikan Oil Drop Experiment

In 1909, American physicist R. Millikan measured the charge of

an electron using negatively charged oil droplets. The measured
charge (e) of an electron is −1.60×10−19 Coulombs.
Using the measured charge of electron, we can calculate the
mass of electron from e/m ratio given by J. J. Thomson’s cathode
ray experiment.
e/m=−1.76×108 Coulomb-per-gram
m=e/−1.76×108
Putting e=−1.60×10−19 Coulomb,
m=9.1×10−28 gram.
11
 Rutherford atomic model
Rutherford atomic model (1911), though a
major breakthrough with a central nucleus
and surrounding electrons, but did not
explain how an electron keeps revolving
around the nucleus without losing energy.

Ernest Rutherford
Rutherford’s Gold Foil Experiment

https://www.youtube.com/watch?v=TMRiZhsY
Le4&t=518s

13
 Sir Earnest Rutherford
His studies with alpha particles allowed him to make a modern
model of the atom.
3 Points to his theory
1. Most alpha particle went through = Atom is mostly empty
space (area of electrons)
2. Some alpha particles bounced straight back = atom has a
solid mass (nucleus)
3. Some alpha particles reflected = nucleus is positively
charged

New Model = Nuclear Model

14
Rutherford’s 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
 Rutherford’s Nuclear Model
• The atom contains a tiny dense center called the
nucleus.
– The volume is about 1/10 trillionth the volume of
the atom.
• The nucleus is essentially the entire mass of
the atom.
• The nucleus is positively charged .
– The amount of positive charge balances the negative
charge of the electrons.
• The electrons move around in the empty space of the
atom surrounding the nucleus.
 Problems with Rutherford’s Nuclear
Model of the Atom
• Electrons are moving charged particles.
• According to classical physics, moving charged
particles give off energy.
• Therefore, electrons should constantly be giving off
energy.
– This should cause the atom to glow!
• The electrons should lose energy, crash into the
nucleus, and the atom should collapse!
– But it doesn’t!
Failure of Rutherford model
The orbiting electron is an accelerating
charge.

Accelerating charges emit

electromagnetic waves and therefore
lose energy

Classical physics predicts electron

should “spiral in” to the nucleus
emitting continuous spectrum of
radiation as the atom “collapses”

CLASSICAL PHYSICS CAN’T GIVE

US STABLE ATOMS………………..
 James Chadwick
Rutherford predicted (in 1920) that another
kind of particle must be present in the
nucleus along with the proton. He predicted
this because if there were only positively
charged protons in the nucleus, then it
should break into bits because of the
repulsive forces between the like-charged
protons! To make sure that the atom stays
electrically neutral, this particle would have
to be neutral itself. In 1932 James Chadwick
discovered the neutron and measured its
mass.
 Subatomic particles of atom
However, this concept of indivisibility of atom did not
hold long and it was proved by the experiments made by
brilliant research workers like J. J. Thompson, Rutherford
(1911), Neil’s Bohr (1912), Chadwick and Moseley and
others that the atom itself has a complex structure.
Atoms consist of several particles called subatomic
particles like the proton, electron, neutron, positron,
neutrino, meson, Higgs boson etc. Out of these,
electrons, protons and neutrons are very important. The
atom remains indivisible though, in all its physical and
chemical changes.
 Subatomic Particles

Mass Charge Charge

Particle
(g) (Coulombs) (units)

Electron (e-) 9.1 x 10-28 -1.6 x 10-19 -1

Proton (p) 1.67 x 10-24 +1.6 x 10-19 +1

Neutron (n) 1.67 x 10-24 0 0

mass p = mass n = 1840 x mass e-

 Atomic Structure
Atoms are composed of
-protons – positively charged particles
-neutrons – neutral particles
-electrons – negatively charged particles

Protons and neutrons are located in the nucleus.

Electrons are found in orbitals surrounding the
nucleus.
 Helium Atom
Shell
proton

+
N
-
+
- N

neutron
electron
 Atomic Structure
Every different atom has a characteristic
number of protons in the nucleus.

atomic number = number of protons

Atoms with the same atomic number have

the same chemical properties and belong
to the same element and Periodic Table
was made on this concept
 Atomic Structure
Each proton and neutron has a mass of
approximately 1 dalton.

The sum of protons and neutrons is the atom’s

atomic mass.

Isotopes – atoms of the same element that

have different atomic mass numbers due to
different numbers of neutrons.
ATOMIC NUMBER (Z) = number of protons in nucleus
MASS NUMBER (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
ISOTOPES are atoms of the same element (X) with different numbers
of neutrons in the nucleus

Mass Number A
Atomic Number Z
X Element Symbol

1 2 3
1 H 1 H (D) 1 H (T)
235 238
92 U 92 U
Isotopes of carbon
Two isotopes of sodium.
 Atomic Structure
Neutral atoms have the same number of protons
and electrons.

Ions are charged atoms.

-cations – have more protons than electrons and
are positively charged
-anions – have more electrons than protons and
are negatively charged
An ion is formed when an atom, or group of atoms, has a
net positive or negative charge (why?).
If a neutral atom looses one or more electrons
it becomes a cation.

11 protons 11 protons
Na 11 electrons Na+ 10 electrons

If a neutral atom gains one or more electrons

it becomes an anion.

17 protons 17 protons
Cl 17 electrons Cl- 18 electrons
 Bohr's model of the atom
Thomson’s atomic model and Rutherford’s atomic
model failed to answer many questions related to the
energy of an atom and its stability. In the year 1913,
Niels Bohr proposed an atomic structure model,
describing an atom as a small, positively charged
nucleus surrounded by electrons that travel in
circular orbits around the positively charged nucleus
as planets around the sun in our solar system, with
attraction provided by electrostatic forces, popularly
known as Bohr’s atomic model. It was basically an
improved version of Rutherford’s atomic
model overcoming its limitations. On most of the
Niels Bohr points, he was in agreement with him, like concepts
of nucleus and electrons orbiting it
The Bohr Model of the Atom
Neils Bohr (1885–1962)
• The nuclear model of the atom does not explain what
structural changes occur when the atom gains or loses
energy.
• Bohr developed a model of the atom to explain how the
structure of the atom changes when it undergoes energy
transitions.
• Bohr’s major idea was that the energy of the atom was
quantized, and that the amount of energy in the atom was
related to the electron’s position in the atom.
– Quantized means that the atom could only have very specific
amounts of energy.
 Bohr’s Model
• The electrons travel in orbits that are at a fixed distance
from the nucleus.
– Stationary states
– Therefore, the energy of the electron was proportional
to the distance the orbit was from the nucleus.
• Electrons emit radiation when they “jump” from an orbit
with higher energy down to an orbit with lower energy.
– The emitted radiation was a photon of light.
– The distance between the orbits determined the energy
of the photon of light produced.
Bohr's model of the atom

electrostatic forces
 Bohr’s Model of the Atom (1913)
1. e- can have only specific
(quantized) energy values
2. light is emitted as e-
moves from one energy
level to a lower energy
level
1
En = -RH ( 2 )
n

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x 10-18J

Salient features of Bohr’s atomic model are:
• Electrons revolve around the nucleus in stable orbits
without emission of radiant energy. Each orbit has a
definite energy and is called energy shell or energy level.
• An electron emits or absorbs energy when it jumps from
one orbit or energy level to another. When it jumps from
higher energy level to lower energy level it emits energy
while it absorbs energy when it jumps from lower energy
level to higher energy level.
• The energy absorbed or emitted is equal to the
difference between the energies of the two energy levels
(E1, E2) and is determined by Plank’s equation.
The Bohr Model of the Atom
 • Plank’s equation
ΔE = E2-E1 = hv
Where,
ΔE = energy absorbed or emitted
h= Plank’s constant
v= frequency of electromagnetic radiation emitted or absorbed

• Angular momentum of an electron revolving in energy

shells is given by:
mevr = nh/2π
Where,
n= number of corresponding energy shell; 1, 2, 3 …..
me= mass of the electron
v= velocity
r=radius
h= Plank’s constant
 Absorption spectrum

Every element has a unique absorption spectrum

 Emission spectrum

Line Emission Spectrum of Hydrogen Atoms

Every element has a unique emission spectrum

 The Bohr Model of the Atom:
Hydrogen Spectrum
• Every hydrogen atom has identical orbits, so every
hydrogen atom can undergo the same energy
transitions.
• However, since the distances between the orbits in
an atom are not all the same, no two leaps in an
atom will have the same energy.
– The closer the orbits are in energy, the lower
the energy of the photon emitted.
– Lower energy photon = longer wavelength.
• Therefore, we get an emission spectrum that has a
lot of lines that are unique to hydrogen.
 Quantum Mechanical Explanation of
Atomic Spectra
• Each wavelength in the spectrum of an atom corresponds to
an electron transition between orbitals.
• When an electron is excited, it transitions from an
orbital in a lower energy level to an orbital in a higher
energy level.
• When an electron relaxes, it transitions from an orbital in a
higher energy level to an orbital in a lower
energy level.
• When an electron relaxes, a photon of light is released whose
energy equals the energy difference between
the orbitals.
 Electron Transitions
• To transition to a higher energy state, the electron
must gain the correct amount of energy corresponding
to the difference in energy between the final and
initial states.
• Electrons in high energy states are unstable and tend
to lose energy and transition to lower
energy states.
• Each line in the emission spectrum corresponds to the
difference in energy between two
energy states.
The Bohr Model of the Atom:
Hydrogen Spectrum
 Bohr showed the energy a H
atom can have is equal to:

1
En = -RH ( n2 )

Ephoton = DE = Ef - Ei
1
Ef = -RH ( 2 )
nf
1
Ei = -RH ( 2 )
ni
1 1
DE = RH ( 2 )
ni n2f
RH is the Rydberg constant
n is the principal quantum number
 Limitations of Bohr Atomic Model Theory:
• It violates the Heisenberg Uncertainty Principle. The Bohr
atomic model theory considers electrons to have both a
known radius and orbit i.e. known position and momentum
at the same time, which is impossible according to
Heisenberg.
• The Bohr atomic model theory made correct predictions for
smaller sized atoms like hydrogen, but poor spectral
predictions are obtained when larger atoms are considered.
• It failed to explain the Zeeman effect when the spectral line
is split into several components in the presence of a
magnetic field.
• It failed to explain the Stark effect when the spectral line
gets split up into fine lines in the presence of electric field.
From Bohr model to Quantum mechanics

• Bohr’s greatest contribution to science was in building

a simple model of the atom.
• It was based on understanding the SHARP LINE
SPECTRA of excited atoms.

But problems existed with Bohr theory —

– theory only successful for the H atom.
– introduced quantum idea artificially.
 Wave Behavior of Electrons
• Light has both wave & particle
properties
• de Broglie (1924) proposed that all
moving objects have wave
properties
• de Broglie predicted that the
L. de Broglie wavelength of a particle was
(1892-1987)
inversely proportional to its
momentum.
• Because it is so small, the wave
character of electrons is
significant.
 de Broglie Equation
• As per Planck’s quantum theory, photon energy is
expressed as,
E = hv
h is Planck’s constant, 6.626 × 10-34 J.s,
E = energy
v = frequency of light, s-1
• Einstein’s famous equation for mass energy
equivalence is
E = 𝒎𝒄𝟐
where c is velocity of light.
 ∴ 𝒉𝒗 = 𝒎𝒄𝟐 … . . 𝑒𝑞. 1
Where, m is mass equivalent of
photon.
𝑐
As, 𝑣 =
𝜆
ℎ𝑐
∴ = 𝑚𝑐 2
𝜆

ℎ
𝜆= … (𝑒𝑞. 2)
𝑚𝑐
The denominator product mc is momentum of a photon (or
particle). If a particle of mass m travels with a velocity 𝑣
then,
𝒉
𝝀= … . . (𝑒𝑞. 3)  de Broglie equation
𝒎𝒗
𝝀 is called de Broglie wave (matter wave)
Calculate wavelength of a) ball weighing 230 g and b)
electron moving with a velocity of 50 metres per second
(Given: electron rest mass, me = 9.107 × 10-31 kg).
According to de Broglie equation,
ℎ
𝜆=
𝑚𝑣

6.626 × 10−34 𝐽. 𝑠
𝜆=
0.23 × 50 m. 𝑠 −1

Hence, 𝜆 = 5.7 × 10-35 m or 5.7 × 10-25 Å (1 Å = 10-10 m)

As, atomic radius is about 10-11 m; above value is small &
difficult to measure
 6.626×10−34 𝐽.𝑠
For electron, 𝜆 =
9.107×10−31 ×50 m.𝑠 −1

= 𝟏. 𝟒𝟓 × 𝟏𝟎−𝟓 𝐦 𝟏. 𝟒𝟔 × 𝟏𝟎𝟓 Å
Find K.E of moving electron with a wavelength of 5.3 pm.
(Given: mass of an electron = 9.11 × 10-31 kg and h = 6.6 × 10-34
J.s)
ℎ
𝑣=
𝑚𝜆
6.6 × 10 −34 𝐽. 𝑠 −12
= −31 −12
(𝑎𝑠 1𝑝𝑚 = 10 m)
9.11 × 10 kg × 5.3 × 10 m
= 1.3682 × 𝟏𝟎𝟖 𝐦𝒔−𝟏
1
K.E of an electron is m𝑣2, thus,
2
9.11 × 10−31 kg × (1.3682 × 108 m𝑠 −1 )2
=
2
= 𝟖. 𝟓𝟐𝟒 × 𝟏𝟎−𝟏𝟓 𝒌𝒈. 𝒎𝟐 𝒔−𝟐
de Broglie supports Bohr
model
ℎ
• de Broglie equation, 𝜆 =
𝑚𝑣
• For stationary wave is that length
of the orbit should be a whole
number multiple of wavelength of
the electron
• If r is the radius of circular orbit,
2𝜋r = 𝑛𝜆
𝑛ℎ 𝑛ℎ
2𝜋r = or, 𝑚𝑣𝑟 = , where, n =
𝑚𝑣 2𝜋
1, 2, 3, and so on.
• angular momentum (𝑚𝑣𝑟) is an
integral multiple of h/2π and is
quantized
Electromagnetic Radiation
 Characterizing Waves
• The amplitude is the height of the wave.
– The distance from node to crest or node
to trough
– The amplitude is a measure of light intensity—the
larger the amplitude, the brighter the light.

• The wavelength (l) is a measure of the

distance covered by the wave.
– The distance from one crest to the next
• The distance from one trough to the next, or the distance
between alternate nodes
Wave Characteristics
 Characterizing Waves
• The frequency (n) is the number of waves that pass a
point in a given period of time.
– The number of waves = the number of cycles.
– Units are hertz (Hz) or cycles/s = s−1 (1 Hz = 1 s−1).

• The total energy is proportional to the amplitude of

the waves and the frequency.
– The larger the amplitude, the more force it has.
– The more frequently the waves strike, the more
total force there is.
 Complementary Properties
• When you try to observe the wave nature of
the electron, you cannot observe its particle
nature, and vice versa.
– Wave nature = interference pattern
– Particle nature = position, which slit it is passing
through
• The wave and particle nature of the electron
are complementary properties.
– As you know more about one you know less about
the other.
 The Relationship Between
Wavelength and Frequency
• For waves traveling at the same speed, the shorter the
wavelength, the more frequently they pass.

• This means that the wavelength and frequency of

electromagnetic waves are inversely proportional.
– Because the speed of light is constant, if we know wavelength
we can find the frequency, and vice versa.
Amplitude and Wavelength
Electromagnetic Spectrum
 Uncertainty Principle
 Problem of defining nature of
electrons in atoms solved by W.
Heisenberg.
 Cannot simultaneously define the
position and momentum (= m•v)
of an electron.
 Dx. Dp = h
 At best we can describe the
W. Heisenberg position and velocity of an electron
1901-1976 by a
 PROBABILITY DISTRIBUTION,
which is given by Y
2
Uncertainty Principle
• Heisenberg stated that the product of the
uncertainties in both the position and speed of a
particle was inversely proportional to its mass.
– x = position, Dx = uncertainty in position
– v = velocity, Dv = uncertainty in velocity
– m = mass
• This means that the more accurately you know the
position of a small particle, such as an electron, the
less you know about its speed, and vice versa.
 Electron Energy

• Electron energy and position are complementary.

– KE = ½mv2
• For an electron with a given energy, the best we
can do is describe a region in the atom of high
probability of finding it.
• Many of the properties of atoms are related to
the energies of the electrons.
Electron Cloud Model/Quantum Mechanics
Model of Atom
Quantum Mechanics Model of Atom is a result of combination
of number of scientific assumptions:
• All particles could be perceived as matter waves with a
wavelength. (Louis de Broglie)
• Principle of uncertainty states that we can't know both the
energy and position of an electron. Therefore, as we learn
more about the electron's position, we know less about its
energy, and vice versa. (Werner Heisenberg)
• There exists more than one energy level of electron in the
atom. Electrons are assigned certain atomic orbitals, that can
differ from one another in energy. (Niels Bohr)
• Erwin Schrödinger, quantum mechanical atomic model
emerged from the solution of Schrödinger's equation for
electron in central electrical field of nucleus
 Quantum or Wave Mechanics
• Schrodinger applied idea of e- behaving
as a wave to the problem of electrons in
atoms.
• Solution to WAVE EQUATION gives set
of mathematical expressions called
WAVE FUNCTIONS, Y
E. Schrodinger
1887-1961 • Contain all information in system
describes an allowed energy state of an
e- .
 Physical significance of Wave
function
• Ψ is a mathematical function for moving particle with no
physical meaning
• Max Born considered electron as a particle and stated that
Ψ2 at any point in space describes the probability of
finding an electron at a point at any given instant, has
physical meaning with +ve value
• Ψ does NOT describe the exact location of the electron.
• Ψ2 is proportional to the probability of finding an e- at a
given point.
For 1 electron, Ψ corresponds to an ORBITAL — the region of
space within which an electron is found.
Schrödinger’s Equation
• Schrödinger’s equation allows us to calculate
the probability of finding an electron with a
particular amount of energy at a particular
location in the atom.
• Solutions to Schrödinger’s equation produce
many wave functions, Y.
• A plot of distance versus Y2 represents an atomic
orbital, a probability distribution map of a region
where the electron is likely to be found.
 Probability and Radial Distribution
Functions
• y 2 is the probability density.
– The probability of finding an electron at a particular point
in space
– For s orbital maximum at the nucleus?
– Decreases as you move away from the nucleus
• The radial distribution function represents the total
probability at a certain distance from the nucleus.
– Maximum at most probable radius
• Nodes in the functions are where the probability drops to
0.
 Probability Density Function
The probability density function represents the total
probability of finding an electron at a particular point in space.
 Radial Distribution Function
The radial distribution function
represents the total probability of
finding an electron within a thin
spherical shell at a distance r from
the nucleus.
The probability at a point
decreases with increasing
distance from the nucleus, but the
volume of the spherical shell
increases.
The net result is a plot that
indicates the most probable
distance of the electron in a 1s
orbital of H is 52.9 pm.
The Time-Independent Schrödinger Equation
• The time-independent equation considers the
electron's quantum state to be unchanging, hence it
considers the electron as a standing wave. The time-
independent equation allows electron densities (i.e.
the sizes and shapes of atomic and
molecular orbitals) to be found using Ψ2, the square
of the wave function.
• The p orbitals below are examples of Ψ2

Px Py Pz
The Time-Independent Schrödinger Equation
The time-independent Schrödinger equation
can be expressed in highly compressed
mathematical shorthand as:

The equation applies to electrons traveling at non-relativistic

speeds. (This means it requires adjustments before it can be
applied high mass elements.) The equation says:
The sum of the Wave Function's Kinetic Energy and Potential Energy
= The Wave Function's Total Energy
The functions Ψ are satisfactory solutions of wave equation only
for certain values of energy E and such values are called eigen
values.
The corresponding functions that are satisfactory solutions of the
equation are called eigen function. Eigen functions should be single
value, finite, continuous for all possible values of three co-
ordinates i.e, x, y and z, including infinity ∞.
The Time-Independent Schrödinger Equation

The time-independent equation can be written in any

suitable coordinate system, such as Cartesian
coordinates (x,y,z). For hydrogenic atoms, spherical
polar coordinates are more suitable, hence:

h is the reduced Planck constant,

m is the electron mass,
is the Laplacian operator,
Ψ is the wave function,
V is the potential energy,
E is the energy eigenvalue,
(r) denotes the quantities are functions of spherical polar coordinates (r, θ, φ)
Solutions to the Wave Function, Y

• Calculations show that the size, shape, and

orientation in space of an orbital are determined
to be three integer terms in the wave function.
– Added to quantize the energy of the electron.
• These integers are called quantum numbers.
– Principal quantum number, n
– Angular momentum quantum number, l
– Magnetic quantum number, ml
– Spin quantum number, s added later
 Quantum Numbers
• Principal quantum number (n) - describes the SIZE of
the orbital or ENERGY LEVEL of the atom.
• Angular quantum number (l) or sublevels - describes
the SHAPE of the orbital.
• Magnetic quantum number (m) - describes an
orbital's ORIENTATION in space.
• Spin quantum number (s) - describes the SPIN or
direction (clockwise or counter-clockwise) in which
an electron spins.
 Principle Quantum Number (n) or Energy
Level
• integer values used to specify the shell/size/level the
electron is in
• describes how far away from the nucleus the electron
shell or level under consideration is
• the lower the number, the closer the energy level is
to the atom's nucleus and less energy
• maximum # of electrons that can fit in an energy level
is given by formula 2n2
 S – orbitals
only holds two electrons
 The Shapes of Atomic Orbitals
• The l quantum number primarily determines the
shape of the orbital.
• l can have integer values from 0 to (n – 1).
• Each value of l is called by a particular letter that
designates the shape of the orbital.
– s orbitals are spherical.
– p orbitals are like two balloons tied at the knots.
– d orbitals are mainly like four balloons tied at the knots.
– f orbitals are mainly like eight balloons tied at the knots.
Angular Quantum Number (l) or Sub-
level
• determines the shape of the orbital
• they are numbered but are also given letters
referring to the orbital type
– l=0 refers to the s-orbitals

– l=1 refers to the p-orbitals

– l=2 refers to the d-orbitals

– l=3 refers to the f-orbitals

 l = 0, the s Orbital

• Each principal energy level

has one s orbital
• Lowest energy orbital in a
principal energy state
• Spherical
• Number of nodes = (n – 1)
 l = 1, p orbitals

• Each principal energy state above n = 1 has three p

orbitals.
– ml = −1, 0, +1
• Each of the three orbitals points along a
different axis
– px, py, pz
• The second lowest energy orbitals in a principal energy
state
• Two-lobed
• One node at the nucleus; total of n nodes
 P – orbitals
holds up to six electrons
P - orbitals

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 l = 2, d Orbitals
• Each principal energy state above n = 2 has five
d orbitals.
– ml = −2, − 1, 0, +1, +2
• Four of the five orbitals are aligned in a different plane.
– The fifth is aligned with the z axis, dz squared.
– dxy, dyz, dxz, dx squared – y squared
• The third lowest energy orbitals in a principal
energy level
• Mainly four-lobed
– One is two-lobed with a toroid
• Planar nodes
– Higher principal levels also have spherical nodes
 D – orbitals
holds up to 10 electrons
 l = 3, f Orbitals

• Each principal energy state above n = 3 has seven d

orbitals.
– ml = −3, −2, −1, 0, +1, +2, +3
• The fourth lowest energy orbitals in a principal
energy state
• Mainly eight-lobed
– Some two-lobed with a toroid
• Planar nodes
– Higher principal levels also have spherical nodes.
 F – orbitals
holds up to 14 electrons
 Orbitals shape

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Magnetic quantum number (m) or Orbitals
• The magnetic quantum number (m) describes the unique quantum
state of an electron. The magnetic quantum number distinguishes
the orbitals available within a subshell, and is used to calculate the
azimuthal component of the orientation of orbital in space.
• Electrons in a particular subshell (such as s, p, d, or f) are defined by
values of ℓ (0, 1, 2, or 3). The value of m can range from -ℓ to +ℓ,
inclusive of zero. Thus the s, p, d, and f subshells contain 1, 3, 5, and
7 orbitals each, with values of m within the ranges 0, ±1, ±2, ±3
respectively.
 Spin quantum number (s)
• the fourth of a set of quantum numbers
• number specifying the direction of the spin of
an electron around its own axis.
– only two electrons of opposite spin may occupy an
orbit
– the only possible values of a spin quantum
number are +1/2 or -1/2.
Table 3-6b Orbitals and Electron Capacity of the First Four Principle Energy
Levels
Number of Maximum
Principle Number of
Type of orbitals number of
energy orbitals
sublevel per electrons
level (n) per type
level(n2) (2n2)
1 s 1 1 2
s 1
2 4 8
p 3
s 1
3 p 3 9 18
d 5
s 1
p 3
4 16 32
d 5
f 7
 Principle
Quantum # (n)
LEVEL/SIZE 1 2 3 4

Angular
s s p s p d s p d f
Quantum # (l)
ORBITAL SHAPE
or SUBLEVEL

Magnetic
Quantum # (m) 1 1 3 1 3 5 1 3 5 7
AXIS/
ORIENTATION
1 4 total 9 total orbitals 16 total orbitals
or ORBITALS
orbital orbitals

Spin Quantum #
(s)
DIRECTION OF
ELECTRON SPIN

2 e- 8 e- 18 e- 32 e-
A periodic table of partial ground-state electron configurations
 Electron Configurations
The electron configuration describes how the electrons are
distributed in the various atomic orbitals.
In a ground state hydrogen atom, the electron is found in the 1s
orbital.
Ground state electron
configuration of hydrogen
principal (n = 1) number of electrons in
1s 1 the orbital or subshell

2s 2p 2p 2p
Energy

angular momentum (l = 0)

The use of an up arrow indicates an electron

with ms = + ½
1s
 Electron Configurations
If hydrogen’s electron is found in a higher energy orbital, the atom
is in an excited state.

A possible excited state electron

configuration of hydrogen

2s 1

2s 2p 2p 2p
Energy

1s
 Electron Configurations
In a multi-electron atoms, the energies of the atomic orbitals are
split.

Splitting of energy levels refers to

the splitting of a shell (n=3) into
subshells of different energies
(3s, 3p, 3d)
 Electron Configurations
According to the Pauli exclusion principle, no two electrons in an
atom can have the same four quantum numbers.

The ground state electron

configuration of helium
2p 2p 2p

2s
1s 2
Energy

Quantum number

Principal (n) 1 1
1s describes the 1s orbital Angular moment (l) 0 0
Magnetic (ml) 0 0
describes the electrons in the 1s orbital Electron spin (ms) +½ ‒½
 Electron Configurations
The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

Li has a total of 3 electrons

The ground state electron

configuration of Li

2p 2p 2p 1s22s1
2s The third electron must go in the
Energy

next available orbital with the

1s lowest possible energy.

The 1s orbital can only accommodate 2

electrons (Pauli exclusion principle)
 Electron Configurations
The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

Be has a total of 4 electrons

The ground state electron

configuration of Be

2p 2p 2p 1s22s2
2s
Energy

1s
 Electron Configurations
The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

B has a total of 5 electrons

The ground state electron

configuration of B

2p 2p 2p
1s 2s 2p
2 2 1
2s
Energy

1s
 Electron Configurations
According to Hund’s rule, the most stable arrangement of
electrons is the one in which the number of electrons with the
same spin is maximized.

C has a total of 6 electrons The ground state electron

configuration of C

1s22s22p2
2p 2p 2p

2s The 2p orbitals are of equal energy, or degenerate.

Energy

1s Put 1 electron in each before pairing (Hund’s rule).

 Electron Configurations
According to Hund’s rule, the most stable arrangement of
electrons is the one in which the number of electrons with the
same spin is maximized.

N has a total of 7 electrons The ground state electron

configuration of N

1s22s22p3
2p 2p 2p

2s The 2p orbitals are of equal energy, or degenerate.

Energy

1s Put 1 electron in each before pairing (Hund’s rule).

 Electron Configurations
According to Hund’s rule, the most stable arrangement of
electrons is the one in which the number of electrons with the
same spin is maximized.

O has a total of 8 electrons The ground state electron

configuration of O

1s22s22p4
2p 2p 2p

2s
Energy

Once all the 2p orbitals are singly occupied, additional

electrons will have to pair with those already in the
1s orbitals.
 Electron Configurations
According to Hund’s rule, the most stable arrangement of
electrons is the one in which the number of electrons with the
same spin is maximized.

F has a total of 9 electrons The ground state electron

configuration of F

1s22s22p5
2p 2p 2p

2s
When there are one or more unpaired electrons, as
Energy

1s in the case of oxygen and fluorine, the atom is

called paramagnetic.
 Electron Configurations
According to Hund’s rule, the most stable arrangement of
electrons is the one in which the number of electrons with the
same spin is maximized.

Ne has a total of 10 electrons The ground state electron

configuration of Ne

1s22s22p6
2p 2p 2p

2s
When all of the electrons in an atom are paired, as
Energy

1s in neon, it is called diamagnetic.

 Electron Configurations
General rules for writing electron
configurations:

1) Electrons will reside in the available

orbitals of the lowest possible energy.

2) Each orbital can accommodate a

maximum of two electrons.

3) Electrons will not pair in degenerate

orbitals if an empty orbital is available.

4) Orbitals will fill in the order indicated

in the figure.
Worked Example 1

Write the electron configuration and give the orbital diagram of a calcium (Ca)
atom (Z = 20).
Setup Because Z = 20, Ca has 20 electrons. They will
fill in according to the diagram at right. Each s subshell
can contain a maximum of two electrons, whereas each p
subshell can contain a maximum of six electrons.

Solution

Ca 1s22s22p63s23p64s2

1s2 2s2 2p6 3s2 3p6 4s2

Remember that the 4s orbital fills before the 3d orbitals.

Electron Configurations and the Periodic Table
The electron configurations of all elements except hydrogen and
helium can be represented using a noble gas core.

The electron configuration of potassium (Z = 19) is

1s22s22p63s23p64s1.

Because 1s22s22p63s23p6 is the electron configuration of argon, we

can simplify potassium’s to [Ar]4s1.
The ground state electron configuration of K:

1s22s22p63s23p64s1

[Ar] [Ar]4s1
Electron Configurations and the Periodic Table
There are several notable exceptions to the order of electron filling
for some of the transition metals.

 Chromium (Z = 24) is [Ar]4s13d5 and not [Ar]4s23d4 as

expected.
 Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.

The reason for these anomalies is the slightly greater stability of d

subshells that are either half-filled (d5) or completely filled (d10).

Cr [Ar]
4s 3d 3d 3d 3d 3d

Greater stability with half-filled

3d subshell
Electron Configurations and the Periodic Table
There are several notable exceptions to the order of electron filling for some of
the transition metals.

 Chromium (Z = 24) is [Ar]4s13d5 and not [Ar]4s23d4 as expected.

 Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.

The reason for these anomalies is the slightly greater stability of d subshells that
are either half-filled (d5) or completely filled (d10).

Cu [Ar]
4s 3d 3d 3d 3d 3d

Greater stability with filled 3d

subshell
 Electronic configuration

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Worked Example 2

Write the electron configuration for an arsenic atom (Z = 33) in the ground state.

Setup The noble gas core for As is [Ar], where Z = 18 2

for Ar.
2 6
The order of filling beyond the noble gas core is 4s, 3d,
and 4p. Fifteen electrons go into these subshells because 2 6 10
there are 33 – 18 = 15 electrons in As beyond its noble gas 2 3
core.

Solution

As [Ar]4s23d104p3

Arsenic is a p-block element; therefore, we should expect its outermost

electrons to reside in a p subshell.
Electron configuration from H Ca (1 20)
 Hybridization
• When atomic orbitals combine to form new set of
equivalent orbitals known as hybrid orbitals.
• Hybrid orbitals will possess different energies and
shapes than combining atomic orbitals
• Hybridization is defined as the process of intermixing
of atomic orbitals of slightly different energies so as to
redistribute their energies, resulting in the formation of
new set of orbitals of equivalent energies and shape.
• It explains the chemical bonding in various compounds
• Due to this hybridization mainly two different kind of
bonds forms,
(i) sigma (σ ) and (ii) pi (π) bond.
 Types of overlapping orbitals
The overlapping atomic orbitals can differ. The two types of
overlapping orbitals are sigma and pi
 Sigma bonds occur when the orbitals of two shared electrons
overlap head-to-head. For example, a bond between two s-
orbital electrons is a sigma bond, because two spheres are
always coaxial. In terms of bond order, single bonds have one
sigma bond
 Pi bonds occur when two orbitals overlap when they are
parallel, double bonds consist of one sigma bond and one pi
bond, and triple bonds contain one sigma bond and two pi
bonds.
 However, the atomic orbitals for bonding may be hybrids. The
methods to get an atomic orbital with the proper character
for the bonding is called hybridization.
 Key points of Valence Bond Theory
• Extends the Lewis concept of electron pair bonds by
introducing the notion of orbital overlap and
hybridization.
• Hybridization is necessary to account for molecular
geometry predicted by Valence Shell Electron Pair
Repulsion Theory (VSEPR)
• Hybrid atomic orbitals are constructed by making
linear combinations (sums and differences) between
hydrogen-like orbitals in the valence shell of each
atom
 Hybridization of Atomic Orbitals
The solutions of Schrodinger equation led to these atomic orbitals.
1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, 4d, 4f, etc.
However, overlap of these orbitals does not give a satisfactory
explanation. In order to explain bonding, these orbitals are
combined to form new set of orbitals – this method is called
hybridization.
sp 2 sp hybrid orbitals from mixing of a s and a p orbital
sp 2 3 sp2 hybrid orbitals from mixing of a s and 2 p orbital
sp3 4 sp3 hybrid orbitals from mixing of a s and 3 p orbital
sp3d 5 sp3d hybrid orbitals from mixing of a s and 3 p and a d
orbital
sp3d 2 ____________

Theories of chemical bonding 121

 Contours and energies of s and  MOs through
combinations of 2p atomic orbitals

end-to-end
overlap

side-to-side
overlap
 Relative energies

s2p < 2p < *2p < s*2p

More effective end-to-end interaction

relative to side-to-side in bonding MOs
 Features
• Number of hybrid orbitals is equal to the
number of the atomic orbitals that get
hybridized.
• Hybridized orbitals are always equivalent in
energy and shape.
• Hybrid orbitals are more effective in forming
stable bonds than the pure atomic orbitals.
• Hybrid orbitals are directed in space in some
preferred direction to have minimum
repulsion between electron pairs and thus a
stable arrangement.
 Hybridization of atomic
orbitals

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• Carbon hybridizes its 2s
and 2p atomic orbitals
to form 4 new sp3
hybrid orbitals
• The four sp3 hybrid
orbitals get directed
towards the four corners
of a tetrahedron that
combines with four
hydrogen atoms
• 25% s-character and
75% p-character in each
sp3 hybrid orbital.
• Angle between sp3
hybrid orbital is 109.28°
(c)
 The sp3 hybrid orbitals in CH4

VSEPR
predicts a
tetrahedral
shape
sp2 hybridization (Boron trichloride)
• Boron ground state configuration: B = ls2, 2s2, 2p1
• B excited state = ls2, 2s1, 2px1, 2py1
• One 2s-orbital of boron intermixes with two 2p-orbitals of excited
boron atom to form three sp2 hybrid orbitals
• Cl atom= 1s2, 2s2, 2p6, 3s2, 3px2, 3py2,3pz1 has one unshared
electron in its p-orbital. Half-filled p-orbitals from three chlorine
atoms overlap head-on with B atom
Boron trichloride (BCl3)
• Involves mixing of
one 2s and two 2p
orbitals forming
three equivalent sp2
hybrid orbitals
• Each sp2 hybrid
orbital has 33.33% s-
character and
66.66% p-character
• Triangular planar
shape with bond
angle of 120°
 The sp2 hybrid orbitals in BF3

VSEPR predicts
a trigonal planar
shape

Compounds involving sp2 hybrid orbitals: BF3,

CO32–, H2CO, H2C=CH2, NO3–, etc
 sp hybridization (Beryllium
chloride)
• Involves mixing of one 2s and one 2pz orbitals
forming two equivalent sp hybrid orbitals
• Be atom ground state
configuration = ls2, 2s2
• Be excited state configuration =
ls2, 2s1, 2p1
• One 2s-orbital and one 2p-orbital
of excited beryllium atom
hybridize to form two sp-
hybridized orbitals (50s:50p)
• Half-filled p-orbitals from two
chlorine atoms overlap head-on
with half-filled hybrid sp-orbitals
of Be to form strong sigma bond.
• Each of the sp hybrid orbital
overlaps with 3pz orbital of
chlorine axially Bond angle of
180° (linear or diagonal)
 Two  Bonds in H–CC–H

A triple bond consists of a sigma and two pi bonds. Overlaps of two sets of
p orbitals form of two  bonds.

Theories of chemical bonding 133

The sp3 hybrid orbitals in NH3

VSEPR predicts
a trigonal
pyramidal shape
The sp3 hybrid orbitals in H2O

VSEPR predicts
a bent (V) shape
 Tutorials

• Calculate wavelength of a) ball weighing 240 g

and b) electron moving with a velocity of 50
metres per second (Given: electron rest mass, me
= 9.107 × 10-31 kg).
• Find K.E of moving electron with a wavelength
of 5.6 pm. (Given: mass of an electron = 9.11 ×
10-31 kg and h = 6.6 × 10-34 J.s)
• Hybridization of following molecules:
• Beryllium hydride, Ethane, boron trifluoride
– Draw the structures
– Write electronic configurations
– State their geometries
– Comment on their properties
Thank you