Created by Turbolearn AI

Discovery of Subatomic Particles

Discovery of Electron
In 1830, Michael Faraday's experiments on the electrolysis of solutions revealed the
particulate nature of electricity. Later, in the mid-1850s, scientists like Faraday began
studying electrical discharge in partially evacuated tubes, which were known as cathode
ray discharge tubes.

The process involves the following:

1. A cathode ray tube is constructed from glass and contains two metal electrodes
that are sealed inside.
2. To enable electrical discharge, the pressure is reduced by evacuating the glass
tubes.
3. A high voltage is applied across the electrodes, causing current to flow as a stream
of particles moves from the negative electrode cathode to the positive electrode
anode. These particles are called cathode rays or cathode ray particles.

4. The anode has a hole in it, and the tube behind the anode is coated with a
phosphorescent material zincsulphide. This allows the flow of current to be
checked.
5. When the rays pass through the anode and strike the zinc sulphide coating, a bright
spot appears.

The path of electrons in a cathode ray tube can be altered using electric and magnetic
fields. The points at which the electron beam strikes the end of the tube can be changed
by using one or both of these fields.

The characteristics of cathode rays are summarized as follows:

Page 1
 Created by Turbolearn AI

Cathode rays originate from the cathode and move towards the anode.
The rays themselves are invisible, but their behavior can be observed using
fluorescent or phosphorescent materials that glow when hit by the rays.
Television picture tubes use cathode rays and fluorescence to produce images on the
screen.
In the absence of electric or magnetic fields, cathode rays travel in straight lines.
In the presence of electric or magnetic fields, the behavior of cathode rays is similar
to that of negatively charged particles, indicating that they consist of electrons.
The characteristics of cathode rays electrons do not depend on the gas present in
the cathode ray tube, suggesting that electrons are a basic constituent of all atoms.

Charge to Mass Ratio of Electron

In 1897, J.J. Thomson measured the ratio of electrical charge e to the mass of an
electron $m $ using a cathode ray tube by applying perpendicular electric and magnetic
e

fields to the path of electrons. The amount of deviation of the particles in the presence of
electrical or magnetic fields depends on:

The magnitude of the negative charge: A greater charge results in greater

interaction with the fields and thus greater deflection.
The mass of the particle: Lighter particles experience greater deflection.
The strength of the electric or magnetic field: Increased voltage across the
electrodes or strength of the magnetic field increases deflection.

Thomson determined the value of e/me as:

11 −1
e/m e = 1.758820×10 C kg

Where:

me is the mass of the electron.

e is the magnitude of the charge on the electron in coulombs C .

Charge on the Electron

R.A. Millikan devised the oil drop experiment 1906 − 1914 to determine the charge on
electrons. He found the charge on an electron to be −1.6×10 C. The currently accepted
−19

value is −1.602176×10 C.
−19

Page 2
 Created by Turbolearn AI

Millikan's oil drop experiment helped determine the charge of a single electron. By
ionizing air in the chamber using X-rays, oil droplets acquired electrical charges through
collisions with gaseous ions. Millikan concluded that the magnitude of electrical charge, q,
on the droplets is always an integral multiple of the electrical charge, e, that is, q = ne,
where n = 1, 2, 3.. .

The mass of the electron $m $ was determined by combining these results with
e

Thomson’s value of the e/m ratio:e

−31
m e = 9.1094×10 kg

Discovery of Proton and Neutron

Electrical discharge in a modified cathode ray tube led to the discovery of canal rays,
which carry positively charged particles. The characteristics of these particles are:

Mass depends on the nature of the gas in the cathode ray tube.
The charge to mass ratio depends on the gas from which they originate.
Some particles carry a multiple of the fundamental unit of electrical charge.
Their behavior in magnetic or electrical fields is opposite to that of electrons.

The smallest and lightest positive ion was obtained from hydrogen and was called a
proton, characterized in 1919. Later, Chadwick 1932 discovered neutrons by bombarding
beryllium with α-particles, resulting in the emission of electrically neutral particles with a
mass slightly greater than that of protons.

Fundamental Particles
The properties of electrons, protons, and neutrons can be summarized in the following
table:

Page 3
 Created by Turbolearn AI

Absolute Relative Approximate

Name Symbol Mass kg Mass u
Charge C Charge Mass u

-1.602176 × 9.109382 ×
Electron e -1 0.00054 0
10-19 10-31
+1.602176 × 1.6726216 ×
Proton p +1 1.00727 1
10-19 10-27
1.674927 ×
Neutron n 0 0 1.00867 1
10-27

Atomic Models

Thomson Model of Atom

In 1898, J.J. Thomson proposed that an atom:

Has a spherical shape with a radius of approximately 10 m.

−10

Has positive charge uniformly distributed.

Has electrons embedded to give the most stable electrostatic arrangement.

This model is also known as the plum pudding, raisin pudding, or watermelon model.
The mass of the atom is assumed to be uniformly distributed.

Thomson's plum pudding model

Thomson's model was able to explain the overall neutrality of the atom, but
was not consistent with later experimental results.

Rutherford’s Alpha-Particle Scattering Experiment

Rutherford's alpha-particle scattering experiment involved bombarding a thin gold foil
with α-particles.

Rutherford's experiment used alpha particles beamed at a thin gold foil. The resulting
scattering patterns revealed crucial information about the structure of atoms, leading to
the development of the nuclear model.

Page 4
 Created by Turbolearn AI

The observations from this experiment were:

1. Most α-particles passed through the gold foil undeflected.

2. A small fraction of α-particles were deflected by small angles.
3. Very few α-particles 1in20, 000 bounced back, deflected by nearly 180°.

Rutherford's conclusions about the structure of the atom:

1. Most of the space in the atom is empty.

2. The positive charge of the atom is concentrated in a very small volume (the
nucleus).
3. The volume occupied by the nucleus is negligibly small compared to the total
volume of the atom.

Rutherford proposed the nuclear model of the atom, in which:

1. The positive charge and most of the mass are densely concentrated in a small region
called the nucleus.
2. The nucleus is surrounded by electrons moving at high speed in circular paths called
orbits.
3. Electrons and the nucleus are held together by electrostatic forces of attraction.

Atomic Number and Mass Number

The atomic number Z is the number of protons in the nucleus of an atom, which is
equal to the number of electrons in a neutral atom.
Atomic number (Z) = number of protons = number of electrons

The mass number A is the total number of protons and neutrons nucleons in the
nucleus of an atom.
Mass number (A) = number of protons (Z) + number of neutrons

Isobars and Isotopes

Isobars: Atoms with the same mass number but different atomic numbers (e.g., ${}
{6}^{14}\text{C}and{}{7}^{14}\text{N}$).
Isotopes: Atoms with identical atomic number but different mass numbers. The
difference between isotopes is due to the presence of different numbers of neutrons
in the nucleus (e.g., ${}{1}^{1}\text{H},{}{1}^{2}\text{D}, and{}_{1}^{3}\text{T}$).

Page 5
 Created by Turbolearn AI

The chemical properties of atoms are controlled by the number of electrons, which is
determined by the number of protons in the nucleus. Therefore, isotopes of a given
element show the same chemical behavior.

Drawbacks of Rutherford Model

1. Stability of the Atom: According to classical mechanics and electromagnetic theory,
an electron moving in an orbit should emit electromagnetic radiation, lose energy,
and spiral into the nucleus, which doesn't happen.
2. Electron Distribution: The model provides no information about the distribution of
electrons around the nucleus or their energies.

Developments Leading to Bohr’s Model

Wave Nature of Electromagnetic Radiation

James Maxwell 1870 explained that when an electrically charged particle moves under
acceleration, it produces alternating electrical and magnetic fields that are transmitted as
electromagnetic waves or electromagnetic radiation. Light is a form of electromagnetic
radiation.

Electromagnetic waves have the following properties:

1. Oscillating electric and magnetic fields are perpendicular to each other and to the
direction of propagation.
2. Electromagnetic waves do not require a medium and can travel in a vacuum.
3. Different types of electromagnetic radiations differ in wavelength λ and frequency ν ,
constituting the electromagnetic spectrum.

The oscillating electric and magnetic fields in an electromagnetic wave have the same
wavelength, frequency, speed, and amplitude, but they vibrate in two mutually
perpendicular planes.

Important parameters to represent electromagnetic radiation:

Page 6
 Created by Turbolearn AI

Frequency ν : The number of waves that pass a given point in one second, measured
in hertz H z, $s $.
−1

Wavelength λ: The distance between two consecutive crests or troughs in a wave,

measured in meters m.
Speed of light c: All types of electromagnetic radiations travel at the same speed in
a vacuum, c = 3.0×10 m s .
8 −1

These parameters are related by the equation:

c = νλ

Wavenumber $v̄$: The number of wavelengths per unit length, typically measured
in cm .
−1

Particle Nature of Electromagnetic Radiation: Planck’s

Quantum Theory
Max Planck proposed Planck’s quantum theory to explain the emission of radiation from
hot bodies and the photoelectric effect. According to Planck:

1. Atoms and molecules can emit or absorb energy only in discrete quantities called
quanta.
2. The smallest quantity of energy that can be emitted or absorbed is called a
quantum.

The energy of a quantum of radiation is proportional to its frequency ν :

E = hν

Where:

E is the energy of the quantum.

h is Planck’s constant $6.626×10 −34
J s$.

Photoelectric Effect
The photoelectric effect occurs when electrons are ejected from a metal surface when it is
struck by a beam of light.

The observations in this experiment were:

Page 7
 Created by Turbolearn AI

1. Electrons are ejected immediately, without any time lag.

2. The number of electrons ejected is proportional to the intensity of light.
3. There is a minimum frequency, ν thresholdf requency, below which the
0

photoelectric effect is not observed.

4. Above the threshold frequency, the kinetic energy of the ejected electrons increases
with the frequency of the light.

Shining a beam of light onto a metal surface can be viewed as shooting a beam of
particles, the photons. Each photon transfers its energy instantaneously to an electron in
the metal, leading to its ejection without delay. The kinetic energy of the ejected electron
is given by:
1 2
me v = hν − hν 0
2

Where:

me is the mass of the electron.

v is the velocity of the ejected electron.

hν is the energy of the striking photon.

hν is the work function $W $ or the minimum energy required to eject an electron.

0 0

Dual Behaviour of Electromagnetic Radiation

Light possesses both particle and wave-like properties, i.e., it has dual behavior.
Depending on the experiment, light behaves either as a wave
interf erenceanddif f raction or as a stream of particles

blackbodyradiationandphotoelectricef f ect.

Electronic Energy Levels: Atomic Spectra

When white light passes through a prism, it spreads out into a series of colored bands
called a spectrum. The spectrum of white light is continuous, with violet merging into
blue, blue into green, and so on.

Page 8
 Created by Turbolearn AI

Emission and Absorption Spectra

Emission Spectrum: The spectrum of radiation emitted by a substance that has
absorbed energy. Atoms, molecules, or ions that have absorbed radiation are said to
be "excited."
Absorption Spectrum: A spectrum formed when white light is passed through a
sample that absorbs radiation at certain wavelengths, leaving dark spaces in the
continuous spectrum.

The study of emission or absorption spectra is referred to as spectroscopy. Emission

spectra of atoms in the gas phase do not show a continuous spread of wavelengths;
instead, they emit light only at specific wavelengths with dark spaces between them.
These spectra are called line spectra or atomic spectra.

The diagram illustrates the basic principles behind emission and absorption spectroscopy,
essential for understanding how elements interact with light.

Each element has a unique line emission spectrum, which can be used to identify
unknown atoms.

Line Spectrum of Hydrogen

The hydrogen spectrum consists of several series of lines, each named after its discoverer.
Balmer showed that the lines in the visible region of the hydrogen spectrum obey the
formula:
1 1 −1
v̄ = 109, 677 ( 2 − 2 )cm
2 n

Where:

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

Page 9
 Created by Turbolearn AI

The series of lines described by this formula are called the Balmer series.

Johannes Rydberg noted that all series of lines in the hydrogen spectrum could be
described by the expression:

1 1 −1
v̄ = 109, 677 ( 2
− 2
)cm
n n
1 2

Where:

n 1 = 1, 2, . . .

n 2 = n 1 + 1, n 1 + 2, . . .

RH is the Rydberg constant for hydrogen.

The first five series of lines that correspond to n = 1, 2, 3, 4, 5 are known as the Lyman,
1

Balmer, Paschen, Brackett, and Pfund series, respectively.

Series n1 n2 Spectral 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

Bohr’s Model for Hydrogen Atom

Niels Bohr 1913 provided a quantitative explanation of the structure of the hydrogen atom
and its spectrum based on Planck’s concept of quantization of energy.

Bohr's postulates for the hydrogen atom are:

Page 10
 Created by Turbolearn AI

1. The electron in the hydrogen atom can move around the nucleus in a circular path of
fixed radius and energy called orbits, stationary states, or allowed energy states.

2. The energy of an electron in the orbit does not change with time. However, the
electron will move from a lower to a higher energy state when it absorbs energy, or
from a higher to a lower energy state when it emits energy.

3. The frequency of radiation absorbed or emitted when a transition occurs between

two stationary states is given by: ΔE = E –E f i

Where:

E1 and E are the lower and higher allowed energy states, respectively.
2

4. The angular momentum of an electron is quantized and can be expressed as:

h
m e vr = n
2π

Where:

n = 1, 2, 3, . . .

me is the mass of the electron

v is the velocity

r is the radius of the orbit

Stationary States and Energy Levels

According to Bohr’s theory:

1. The stationary states for an electron are numbered n = 1, 2, 3, . . ., known as

principal quantum numbers.

2. The radii of the stationary states are expressed as: rn = n a0

2

Where:

a0is the radius of the first stationary state, called the Bohr orbit, which is 52.9
pm.

3. The energy of the stationary state is given by: E n = −R H (

1

n
2
)

Where:

RH is the Rydberg constant, with a value of 2.18×10 −18

.
J

Page 11
 Created by Turbolearn AI

Explanation of Line Spectrum of Hydrogen

The line spectrum observed in the case of hydrogen can be quantitatively explained using
Bohr’s model. Radiation is absorbed if the electron moves from an orbit of smaller
principal quantum number to an orbit of higher principal quantum number, and radiation
is emitted if the electron moves from a higher orbit to a lower orbit. The energy gap
between the two orbits is given by:

1 1
ΔE = E f –E i = R H ( 2
− 2
)
n n
i f

The frequency of the emitted or absorbed photon can be evaluated using:

RH 1 1 7 1 1 −1
v̄ = ( 2
− 2
) = 1.09677×10 ( 2
− 2
)m
hc n n n n
i f i f

Limitations of Bohr’s Model

1. It fails to account for the finer details of the hydrogen atom spectrum, such as
doublets.
2. It cannot explain the spectrum of atoms other than hydrogen, such as helium.
3. It is unable to explain the splitting of spectral lines in the presence of magnetic
Zeemanef f ect or electric fields Starkef f ect.

4. It cannot explain the ability of atoms to form molecules by chemical bonds.

Towards Quantum Mechanical Model of the

Atom
Two important developments contributed to the formulation of a more suitable and
general model for atoms:

1. Dual behavior of matter

2. Heisenberg uncertainty principle

Dual Behavior of Matter

Louis de Broglie proposed that matter, like radiation, should exhibit dual behavior, i.e.,
both particle and wave-like properties. The relationship between wavelength λ and
momentum p of a material particle is given by:
h h
λ = =
p mv

Page 12
 Created by Turbolearn AI

Where:

m is the mass of the particle.

v is the velocity.

p is its momentum.

Heisenberg Uncertainty Principle

Werner Heisenberg stated the uncertainty principle, which says that it is impossible to
determine simultaneously the exact position and exact momentum orvelocity of an
electron. Mathematically, this principle can be expressed as:
h
Δx×Δp x ≥
4π

Where:

Δx is the uncertainty in position.

Δp x is the uncertainty in momentum.

Heisenberg Uncertainty Principle

Werner Heisenberg, a German physicist, introduced the uncertainty principle in 1927, a
consequence of the dual behavior of matter and radiation.

It's impossible to determine simultaneously the exact position and exact

momentum orvelocity of an electron.

Mathematically, this principle is expressed as:

Δx ∗ Δpx ≥ h/4π

Where:

Δx is the uncertainty in position

Δpx or$ Δ vx$ is the uncertainty in momentum orvelocity

Implications

Page 13
 Created by Turbolearn AI

If the position of an electron is known with high accuracy small$ Δ x$, its velocity
becomes uncertain large$ Δ vx$.
Conversely, if the velocity is precisely known small$ Δ vx$, the position becomes
uncertain large$ Δ x$.
Measurements on an electron's position or velocity will always yield a "fuzzy" or
blurred picture.

Understanding with an Analogy

Measuring the thickness of paper with an unmarked meter stick yields inaccurate results.
Similarly, determining an electron's position requires a "meterstick" calibrated in units
smaller than the electron itself.

To "observe" an electron, we must illuminate it with "light" or electromagnetic radiation

with a wavelength smaller than the electron's dimensions. However, high-energy photons
would alter the energy of the electrons upon collision. Calculating the electron's position
becomes possible, but the velocity after the collision remains largely unknown.

Significance
The Heisenberg Uncertainty Principle rules out the existence of definite paths or
trajectories for electrons and other similar particles. Trajectories are determined by
location and velocity at various moments. For sub-atomic objects like electrons,
determining position and velocity simultaneously with arbitrary precision is impossible.
Thus, we cannot speak of an electron's trajectory.

Macroscopic vs. Microscopic Objects

The effect of the Heisenberg Uncertainty Principle is significant only for the motion of
microscopic objects. For macroscopic objects, it is negligible.

For an object of mass 10 −6

kg:
−29 2 −1
Δv ∗ Δx ≈ 5 ∗ 10 m s

This uncertainty is insignificant for milligram-sized or heavier objects.

In contrast, for an electron $m = 9.11 ∗ 10 −31

:
$kg

−5 2 −1
Δv ∗ Δx ≈ 5.79 ∗ 10 m s

Page 14
 Created by Turbolearn AI

If the exact location of the electron is known to an uncertainty of only 10 −8

m, then the
uncertainty Δv in velocity would be:
6 −1
Δv ≈ 5.79 ∗ 10 ms

This is so large that the concept of electrons moving in fixed Bohr orbits cannot hold.
Precise statements of position and momentum must be replaced by statements of
probability.

Examples
Problem 2.16 A microscope employed to locate an electron in an atom within a
distance of 0.1 Å. What is the uncertainty involved in the measurement of its
velocity? Solution - ∆ x∆p
Problem 2.16 - A golf ball has - The uncertainty
= 0.579×107ms–1(1J = 1kgm2s–2) = 5.79×106ms–1P roblem2.16 of 45 m/s. If the

speed can be measured within accuracy of 2%, calculate the uncertainty in the
position. Solution Using the equation 2.22 = 1.46×10–33 m This is nearly ~ 1018
times smaller than the diameter of a typical atomic nucleus. As mentioned earlier for
large particles, the uncertainty principle sets no meaningful limit to the precision
measurements.

Heisenberg's Background
Max Born: University of Munich in 1923
Worked with Born at Gottingen and Niels Bohr in Copenhagen
Professor of physics at the University of Leipzig from 1927 to 1941
In charge of German research on the atomic bomb during World War II
Director of Max Planck Institute for physics in Gottingen after the war
Accomplished mountain climber
Awarded the Nobel Prize in Physics in 1932

Quantum Mechanical Model of the Atom

The failure of the Bohr model, which regarded the electron as a charged particle moving
in well-defined circular orbits, led to the development of quantum mechanics.

Key Concepts

Page 15
 Created by Turbolearn AI

Classical mechanics fail when applied to microscopic objects like electrons, atoms,
and molecules because it ignores the dual behavior of matter and the uncertainty
principle.
Quantum mechanics accounts for the dual behavior of matter, dealing with the
motion of microscopic objects with both wave-like and particle properties.

Quantum mechanics was developed independently in 1926 by Werner Heisenberg and

Erwin Schrödinger.

Erwin Schrödinger, an Austrian physicist, received his Ph.D. in theoretical physics from the
University of Vienna in 1910.

Schrödinger succeeded Planck at the University Berlin at Planck’s request. In 1933,

Schrödinger left Berlin because of opposition to Hitler Nazi policies and returned to
Austria in 1936. After invasion by Germany, Schrödinger was forcibly removed from his
professorship. He then moved to Dublin, Ireland where he remained for seventeen years.
Schrödinger shared the Nobel Prize for Physics with P.A.M. Dirac in 1933.

Schrödinger Equation
The fundamental equation of quantum mechanics, developed by Schrödinger,
incorporates the wave-particle duality of matter. For a system whose energy does not
change with time, the Schrödinger equation is:

Ĥψ = Eψ

Where:

Ĥ is the Hamiltonian operator

E represents energy

ψ is the wave function

Solving the Schrödinger equation for the hydrogen atom yields possible energy levels and
corresponding wave functions $ψ$ for the electron. These quantized energy states are
characterized by three quantum numbers:

1. Principal quantum number n

2. Azimuthal quantum number l
3. Magnetic quantum number $m l$

Atomic Orbitals

Page 16
 Created by Turbolearn AI

Wave functions for hydrogen or hydrogen-like species with one electron are called atomic
orbitals. The probability of finding an electron at a point within an atom is proportional to
|ψ| at that point.
2

Applying the Schrödinger equation to multi-electron atoms is challenging, but

approximate methods and modern computers show that orbitals in other atoms do not
radically differ from hydrogen orbitals. Energies of orbitals in multi-electron atoms
depend on quantum numbers n and l.

Quantum Mechanical Model Features

1. Quantized Energy: Electrons in atoms have specific energy values when bound to
the nucleus. These energy levels result from the wave-like properties of electrons
and the solutions of the Schrödinger wave equation.
2. Uncertainty: Exact position and velocity of an electron cannot be determined
simultaneously. We can only discuss the probability of finding the electron at
different points in an atom.
3. Atomic Orbital: The wave function ψ for an electron in an atom. When an electron is
described by a wave function, it occupies that orbital. Many such wave functions are
possible, leading to many atomic orbitals in an atom, which form the basis of the
electronic structure of atoms. Each orbital has a definite energy and can contain no
more than two electrons. In multi-electron atoms, electrons fill orbitals in increasing
energy order.
4. Wave Function: All information about the electron is stored in its orbital wave
function ψ, and quantum mechanics allows us to extract this information.
5. Probability Density: The probability of finding an electron at a point within an atom
is proportional to |ψ| at that point. This is the probability density, always positive,
2

and helps predict the region around the nucleus where the electron is most likely to
be found.

Orbitals and Quantum Numbers

Orbitals are distinguished by quantum numbers, each designated by three quantum
numbers labeled as n, l, and m .l

Page 17
 Created by Turbolearn AI

Principal Quantum Number $n$:

A positive integer: n = 1, 2, 3, . . .
Determines the size and energy of the orbital.
Identifies the shell.
For hydrogen atoms, energy and size depend only on n.
As n increases, the number of allowed orbitals increases, given by n . 2

All orbitals of a given n form a single shell, represented by letters:

n 1 2 3 4 ...

Shell K L M N ...

The size of an orbital increases with n, meaning the electron is located farther from
the nucleus. Energy increases with n because more energy is required to move a
negatively charged electron away from the positively charged nucleus.

Azimuthal Quantum Number $l$:

Also known as orbital angular momentum or subsidiary quantum number.

Defines the three-dimensional shape of the orbital.
For a given n, l can have n values ranging from 0 to n–1: l = 0, 1, 2, . . . , (n–1)
Each shell consists of one or more sub-shells or sub-levels. The number of
sub-shells equals the value of n.
Value for l: 0 1 2 3 4 5 ...

Notation: s p d f g h ...

Magnetic Orbital Quantum Number $m $: l

Provides information about the spatial orientation of the orbital with respect to
a standard set of coordinate axes.
For any sub-shell def inedby$l$value, 2l + 1 values of m are possible.
l

These values are given by: m = –l, –(l–1), –(l–2). . . 0, 1.. . (l–2), (l–1), l
l

Value of l ml values Number of Orbitals

0 0 1 onesorbital
1 –1, 0, +1 3 threeporbitals
2 –2, –1, 0, +1, +2 5 f ivedorbitals

The values of m are derived from l, and the values of l are derived from n. Each
l

orbital is defined by a set of values for n, l, and m . l

For example, an orbital described by the quantum numbers n = 2, l = 1, m l = 0 is

an orbital in the p sub-shell of the second shell.

Page 18
 Created by Turbolearn AI

Electron Spin $s$:

In 1925, George Uhlenbeck and Samuel Goudsmit proposed the fourth

quantum number, the electron spin quantum number $m $. s

An electron spins around its own axis, similar to how the Earth spins while
revolving around the Sun.
An electron has an intrinsic spin angular momentum, which can have two
orientations relative to a chosen axis.
These orientations are distinguished by the spin quantum numbers m , which
s

can take values of +½ or –½.

These are called the two spin states of the electron, represented by arrows: ↑
spinup and ↓ spindown.

Two electrons with different m values are said to have opposite spins.
s

An orbital cannot hold more than two electrons, and these two electrons must
have opposite spins.

In summary, the four quantum numbers provide the following information:

1. n defines the shell, determines the size of the orbital, and largely determines the
energy of the orbital.
2. l identifies the subshell and determines the shape of the orbital. There are (2l + 1)
orbitals of each type in a subshell: one s orbital $l = 0$, three p orbitals $l = 1$, and
five d orbitals $l = 2$ per subshell.
3. m designates the orientation of the orbital.
l

4. m refers to the orientation of the spin of the electron.

s

Quantum Number Symbol Determines

Principal n Shell, size, and energy

Azimuthal l Subshell and shape
Magnetic ml Orientation in space
Spin ms Spin orientation

What Orbitals Are NOT

Page 19
 Created by Turbolearn AI

Feature Orbit Atomic Orbital

Proposed by Bohr; a circular path Quantum mechanical concept; refers to

Definition around the nucleus in which an the one-electron wave function ψ in an
electron moves. atom.
Characterized by three quantum
Precise description of the path of the numbers $n, l, m $ and its value
Description
l

electron. depends upon the coordinates of the

electron.
Not possible; contradicts
Heisenberg Considers it
Heisenberg's uncertainty principle
Bohr orbits have no real meaning
Physical ψ has no physical meaning by itself.
and their existence can never be
Meaning The square of the wave function, $
demonstrated experimentally.
Probability N/A $

Examples
Problem 2.17 What is the number of orbitals associated with the principal quantum
number n = 3 ? Solution 0, 1 and 2. Thus there is one 3s orbital
n = 3, l = 0andml = 0; there are three 3p orbitals n = 3, l = 1andml = –1, +1; there

are five 3d orbitals n = 3, 2andml = –2, –1, 0, +1+, +2. Therefore, the total number
of orbitals is 1+3+5 = 9 The same value can also be obtained using the relation;
number of orbitals = n2, i.e. 32 = 9.
Problem 2.18 Using s, p, d notations, describe the orbital with the following
quantum numbers a n = 2, l = 1, b n = 4, l = 0, c n = l = 3, d n = 3, l = 2 Solution | a) 2
1 2p b) 4 0 4s c) 5 3 5f d) 3 2 3d |

Visualizing Atomic Orbitals

Page 20
 Created by Turbolearn AI

The orbital wave function, ψ, has no physical meaning. However, plots of the
corresponding wave functions as a function of r thedistancef romthenucleus differ for

different orbitals.

The image includes graphs of wave functions ψr and probability density ψ2r for 1s and
2s orbitals.

Max Born and Probability Density

According to Max Born, the square of the wave function $ψ $ at a point gives the
2

probability density of the electron at that point. The variation of ψ as a function of r

2

differs for 1s and 2s orbitals. For the 1s orbital, the probability density is maximum at the
nucleus and decreases sharply as we move away from it. For the 2s orbital, the
probability density first decreases sharply to zero, then increases again, reaching a small
maxima before decreasing and approaching zero as r increases.

Nodes
The region where the probability density function reduces to zero is called nodal surfaces
or nodes. An ns-orbital has (n–1) nodes, meaning the number of nodes increases with the
principal quantum number n.

Charge Cloud Diagrams

Page 21
 Created by Turbolearn AI

The image above shows charge cloud diagrams and boundary surface diagrams for 1s
and 2s orbitals. Probability density variation can be visualized using charge cloud
diagrams.

Boundary Surface Diagrams

Boundary surface diagrams represent the shapes of orbitals by drawing a contour surface
in space on which the value of probability density |ψ| is constant. For a given orbital, the
2

boundary surface diagram encloses a region or volume within which the probability of
finding the electron is very high e. g. , 90.

The boundary surface diagram for an s orbital is a sphere centered on the nucleus. All s-
orbitals are spherically symmetric, meaning the probability of finding the electron at a
given distance is equal in all directions. The size of the s orbital increases with n, with the
electron located further away from the nucleus.

p Orbitals

Page 22
 Created by Turbolearn AI

Boundary surface diagrams for three 2p orbitals $l = 1$ are not spherical. Instead, each p
orbital consists of two sections called lobes on either side of the plane that passes
through the nucleus.

The size, shape, and energy of the three p orbitals are identical. They differ in the way the
lobes are oriented. Since the lobes may be considered to lie along the x, y, or z axis, they
are given designations 2p , 2p , and 2p .
x y z

As with s orbitals, p orbitals increase in size and energy with the principal quantum
number. The number of nodes is given by n–2.

d Orbitals

For l = 2, the orbital is known as a d-orbital, and the minimum value of the principal
quantum number n has to be 3. There are five m values –2, –1, 0, +1, and + 2, and thus
l

there are five d orbitals.

The five d-orbitals are designated as d , d , d , d

yz xz , and d . The shapes of the first
xy
2
x –y
2
z
2

four d-orbitals are similar, whereas the d orbital is different from the others. All five 3d
z
2

orbitals are equivalent in energy.

Page 23
 Created by Turbolearn AI

The d orbitals for which n is greater than 3 4d, 5d. . . have similar shapes to 3d orbitals but
differ in energy and size. In addition to radial nodes, the probability density functions for
np and nd orbitals are zero at the planes passing through the nucleus.

Energies of Orbitals

Hydrogen Atom

The energy of an electron in the hydrogen atom is solely determined by the principal
quantum number. The energy increases as follows:

1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f <. . .

Orbitals with the same energy are called degenerate. The 1s orbital corresponds to the
most stable condition and is called the ground state. An electron in the 2s, 2p, or higher
orbitals is in an excited state.

Multi-Electron Atoms
The energy of an electron in a multi-electron atom depends not only on its principal
quantum number $n$ but also on its azimuthal quantum number $l$. For a given principal
quantum number, the energy of orbitals increases in the order s < p < d < f .

For higher energy levels, these differences are pronounced, leading to staggering of
orbital energy, e.g., 4s < 3d and 6s < 5d; 4f < 6p. The main reason for different energies
of subshells is mutual repulsion among electrons.

Page 24
 Created by Turbolearn AI

In multi-electron atoms, the total attractive interactions are more than the repulsive
interactions. The repulsive interaction of electrons in the outer shell with those in the
inner shell is more important. The attractive interactions increase with the positive charge
$Z $ on the nucleus.
e

Shielding Effect
Electrons in inner shells partially screen the positive charge on the nucleus, so the outer
electrons experience a net positive charge, called the effective nuclear charge $Z $.ef f

Despite the shielding, the attractive force experienced by outer shell electrons increases
with the nuclear charge.

Dependence on Shell and Shape

Attractive and repulsive interactions depend on the shell and shape of the orbital.
Electrons in spherical s orbitals shield outer electrons more effectively than electrons in p
orbitals. Within a shell, due to the spherical shape of the s orbital, the s orbital electron
spends more time close to the nucleus.

In other words, for a given shell principalquantumnumber, the energy experienced by the
electron decreases with an increase in the azimuthal quantum number: s > p > d. The
extent of shielding leads to splitting of energy levels within the same shell, meaning the
energy depends on n and l.

A simple rule states that 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 the lower value of n
will have the lower energy. Also, energies of orbitals in the same subshell decrease with
an increase in the atomic number $Z $.ef f

Filling of Orbitals in Atoms

The filling of electrons into different atoms follows the Aufbau principle, which is based
on the Pauli exclusion principle, Hund's rule of maximum multiplicity, and the relative
energies of the orbitals.

Aufbau Principle

Page 25
 Created by Turbolearn AI

In the ground state of atoms, orbitals are filled in order of increasing energies. Electrons
first occupy the lowest energy orbital available and enter higher energy orbitals only after
the lower energy orbitals are filled.

The order of energies of orbitals is extremely useful:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f , 5d, 6p, 7s. . .

Pauli Exclusion Principle

No two electrons in an atom can have the same set of four quantum numbers.

Only two electrons may exist in the same orbital, and these electrons must have opposite
spins.

Hund's Rule of Maximum Multiplicity

Pairing of electrons in the orbitals belonging to the same subshell degenerateorbitals
does not take place until each orbital in that subshell has one electron each
i. e. , issinglyoccupied.

Half-filled and fully filled degenerate sets of orbitals acquire extra stability due to their
symmetry.

Page 26
 Created by Turbolearn AI

Electronic Configuration of Atoms

The distribution of electrons into orbitals of an atom is called its electronic configuration. It
can be represented in two ways:

1. s p d . . . notation
a b c

2. Orbital diagram

In the first notation, the subshell is represented by the respective letter symbol, and the
number of electrons present in the subshell is depicted as a superscript a, b, c, . . .. The
orbital picture represents each orbital of the subshell as a box, with electrons represented
by arrows ↑ or ↓ indicating positive or negative spin.

Stability of Completely Filled and Half-Filled Subshells

The ground state electronic configuration corresponds to the state of the lowest total
electronic energy. In certain elements like Cu or Cr, an electron shifts from a subshell of
lower energy 4s to a subshell of higher energy 3d if such a shift results in all orbitals of
the subshell of higher energy getting either completely filled or half-filled.

There is extra stability associated with these electronic configurations due to:

1. Symmetrical distribution of electrons: Symmetry leads to stability. Symmetrical

distribution minimizes shielding and maximizes attraction by the nucleus.
2. Exchange Energy: The stabilizing effect arises when two or more electrons with the
same spin are present in degenerate orbitals of a subshell. These electrons tend to
exchange their positions, releasing exchange energy. The number of exchanges is
maximum when the subshell is either half-filled or completely filled, leading to
maximum exchange energy and stability.

Page 27