Atomic Structure

Dr. Md. Mahbub Alam

Department of Chemistry
BUET, Dhaka-1000

The contents of this presentation is made to provide a brief idea about the topic, details will be discussed in the
classes. Contents have been collected from multiple textbooks and internet.
© Department of Chemistry, BUET
Theories for Atomic Structure in History
• Dalton’s

• Thomson’s

• Rutherford’s

• Bohr’s

• Quantum Mechanical (QM)

• Heisenberg; Schrodinger; Planck; Einstein, etc.

© Department of Chemistry, BUET

John Dalton’s Atomic Theory
• Background:
- (1766-1844)
- Born in England
- Belonged to The Royal Society
- Is said to one of the top 50 most influential persons in history.
• Experiment-
- Measured Atomic Weight, and came up with The Atomic Theory.

Postulates:
 All matter is made of atoms. Atoms are indivisible and indestructible.
 All atoms of a given element are identical in mass and properties; atoms
of different elements are different from each other.
 Compounds are formed by a combination of two or more different kinds of
atoms in simple whole number ratios.
 A chemical reaction is a rearrangement of atoms.
© Department of Chemistry, BUET
Limitations of Dalton’s Atomic Theory
 It was proved that an atom is not indivisible. As an atom can be
subdivided into electrons, protons and neutrons.
 Atoms of several elements differ in their densities and masses. These
atoms with the different masses are known as isotopes. For example,
Chlorine (Cl) has 2 isotopes with the mass numbers of 35 and 37.
 According to Dalton Atomic Theory, when atoms of different elements
(atoms of two or more elements) combine in simple whole number ratios,
we get chemical compounds. But this is not true in case of complex
organic compounds. For example, sucrose (C12H22O11)

© Department of Chemistry, BUET

Earnest Rutherford’s Atomic Theory
• Background:
- (1871-1937)
- Born In New Zealand
- Nobel prize in Chemistry - 1908
- Knighted – 1914
- Rutherfordium (Rf) was named after him

• Experiment-
- shot alpha particles at gold foil
- noticed some went right through, and others came
out at an angel or bounced directly back

© Department of Chemistry, BUET

Observations of the Gold Foil Experiment
 Major space in an atom is empty – A large fraction of α-
particles passed through the gold sheet without getting
deflected. Therefore, the major part of an atom must be
empty.

 The positive charge in an atom is not distributed

uniformly and it is concentrated in a very small volume.

Rutherford’s Gold Foil Experiment

 Very few α-particles had deflected at large angles or deflected back. Moreover,
very few particles had deflected at 180o. Therefore, he concluded that the
positively charged particles covered a small volume of an atom in comparison to
the total volume of an atom.

© Department of Chemistry, BUET

Earnest Rutherford’s Atomic Theory
 An atom is composed of positively charged particles.
Majority of the mass of an atom was concentrated in a
very small region. This region of the atom was called as
the nucleus of an atom.
 Atoms nucleus is surrounded by negatively charged particles
called electrons. The electrons revolve around the nucleus
in a fixed circular path at very high speed. These fixed
circular paths were termed as “orbits.”
 An atom has no net charge or they are electrically neutral because electrons are
negatively charged and the densely concentrated nucleus is positively charged.
 The size of the nucleus of an atom is very small in comparison to the total size of
an atom.

© Department of Chemistry, BUET

 Limitations of Rutherford Atomic Model
 According to Rutherford’s postulate, electrons revolve at a very high speed
around a nucleus of an atom in a fixed orbit. However, Maxwell explained
accelerated charged particles release electromagnetic radiations. Therefore,
electrons revolving around the nucleus will release electromagnetic radiation.

 The electromagnetic radiation will have energy from the electronic motion as a
result of which the orbits will gradually shrink. Finally, the orbits will shrink
and collapse in the nucleus of an atom.

© Department of Chemistry, BUET

Niels Bohr’s Atomic Model
• Background:
- (1885-1962)
- Born In Denmark
- Nobel prize in Physics - 1922
- Founded the Institute of Theoretical Physics - 1920
- Introduced The Quantum Theory

Bohr’s postulates
 In an atom, electrons revolve around the positively charged nucleus in a definite
circular path called as orbits or shells.
 The angular momentum of an electron revolving around the
nucleus in an orbit is integer multiple of h/2π.

mvr = nh/2π n = 1, 2, 3, 4, ……
 The electrons in an atom move from a lower energy level to a
higher energy level by gaining the required energy and an
electron moves from a higher energy level to lower energy level
E = E1 − E2 = hν
by losing energy.
© Department of Chemistry, BUET
Niels Bohr’s Atomic Model

© Department of Chemistry, BUET

Limitations of Bohr’s Atomic Theory
• It could not explain the spectra obtained from larger atoms.

• It violates the Heisenberg Uncertainty Principle.

• Failed to explain the Zeeman Effect (effect of magnetic field on the spectra
of atoms) and Stark effect (effect of electric field on the spectra of atoms).

© Department of Chemistry, BUET

Niels Bohr’s Atomic Model – Radius of an Orbit
Charge of nucleus = Ze
Attraction force between electron and nucleus = Ze.e/r2 = Ze2/r2
The attraction force is counterbalanced by the centrifugal force = mv2/r

Therefore, Ze2/r2 = mv2/r

or, v2 = Ze2/mr………………..(1) v
electron
According to Bohr’s postulate, r
mvr = nh/2π
or, v2 = n2h2/4π2m2r2………....(2) nucleus

From equation (1) and (2),

r = n2h2/4π2mZe2

© Department of Chemistry, BUET

 Niels Bohr’s Atomic Model – Calculating Energy
Total energy E of an electron in any orbit, We know, mv2/r = Ze2/r2
E = K.E. + P.E. Therefore, E = Ze2/2r – Ze2/r
= ½ mv2 + (-Ze2/r) = - Ze2/2r
Substituting the value of r,

E = - 2π2mZ2e4/n2h2 ; E = - RH/n2 ; RH (Rydberg constant), = 2.178 x 10-18 J

 An electron in a higher energy level (initial energy level, Ei) undergoes a

transition to a lower energy level (final energy level, Ef). In this process, the
electron loses energy, which is emitted as a photon.
Then, Ei = - RH/ni2 ; Ef = - RH/nf2 ;
ΔE = - RH(1/nf2 - 1/ni2) = RH(1/ni2 - 1/nf2)
For the wavelength (λ) of the radiation, the equation will be,
1/λ = RH(1/ni2 - 1/nf2) ; RH = 10973731 m-1
© Department of Chemistry, BUET
 Calculating Energy and Wavelength of an Electron
Problem: What is the wavelength of light emitted when the electron in a hydrogen atom
undergoes a transition from energy level n = 4 to level n = 2?

© Department of Chemistry, BUET

Calculating Energy and Wavelength of an Electron
Problem: Calculate the shortest and longest wavelengths of Balmer series of hydrogen atom.
Given R =1.097×107 m-1.

Problem: A hydrogen atom absorbs a photon of UV light and its electron enters the n = 4
energy level. Calculate (a) the change in energy of the atom and (b) the wavelength (in nm) of
the photon.

© Department of Chemistry, BUET

Heisenberg Uncertainty Principle
‘It is impossible to know simultaneously both the momentum p (defined as
mass times velocity) and the position of a particle with certainty’.

© Department of Chemistry, BUET

Wave nature of Light
 Wavelength,  is the distance between identical points on successive waves.
 Frequency,  is the number of waves that pass through a particular point in 1 second.
 Amplitude is the vertical distance from the midline of a wave to the peak.

 c is the speed of light waves in a vacuum is 3.00 × 108 m/s

© Department of Chemistry, BUET

Obtaining the Wavelength of Light from its Frequency
Problem 1. What is the wavelength of the yellow sodium emission, which has a
frequency of 5.09 × 1014/s?

Similarly, you can obtain the frequency of light from its wavelength

© Department of Chemistry, BUET

Obtaining the Frequency of Light from its Wavelength

Problem:

© Department of Chemistry, BUET

Electromagnetic Spectrum
 The range of frequencies or wavelengths of electromagnetic radiation is called the
electromagnetic spectrum.

© Department of Chemistry, BUET

Quantization of Energy
 When solids are heated, they emit electromagnetic radiation over a wide range of
wavelengths.
 It is assumed that atoms and molecules could emit (or absorb) any arbitrary amount
of radiant energy.
 Planck said that atoms and molecules could emit (or absorb) energy only in discrete
quantities, like small packages or bundles.

 Planck gave the name quantum to the

smallest quantity of energy that
can be emitted (or absorbed) in the
form of electromagnetic radiation.

E = hv
h is Planck constant, v is frequency

 Energy is always emitted in integral multiples of hv; i.e., E = nhv

Where, n = 1, 2, 3, ...
© Department of Chemistry, BUET
Photoelectric Effect
 The photoelectric effect is the emission of electrons when electromagnetic
radiation, such as light, hits a material.
 Electrons emitted in this manner are called photoelectrons.
 To cause the emission of electron, the light (now called photon) should have a
certain minimum frequency, called the threshold frequency.

© Department of Chemistry, BUET

Calculating Energy of a Photon
E = hv and c =vλ i.e., speed of light = frequency x wavelength

Problem

© Department of Chemistry, BUET

Calculating Energy of a Photon
Problem

© Department of Chemistry, BUET

Dual nature of electrons
An electron moving in a close orbit is considered as a stationary or
standing wave.

Therefore, according to Planck’s equation,

E = hν ;h is Planck’s constant, ν is frequency

Using Einstein’s equation,

E = mc2 ;m is the mass, c is velocity
If r is the radius of orbit, and n is the

Therefore, number of wave

mc2 = hν Therefore, the circumference,

or, mc = hν/c = h/λ 2πr= nλ

or, λ = h/mc or, λ = 2πr/n…………… (2)

or, λ = h/mv………….. (1) ;For electron, velocity c = v From equation (1) and (2),

λ is known as de Broglie wavelength. 2πr/n = h/mv

or, mvr = nh/2π
© Department of Chemistry, BUET
Dual nature of electrons
a. Calculate the wavelength (in meters) of the wave associated with a 1.00-kg mass
moving at 1.00 km/hr. b. What is the wavelength (in picometers) associated with an
electron, whose mass is 9.11 × 10-31 kg, traveling at a speed of 4.19 × 106 m/s?

© Department of Chemistry, BUET

Dual nature of electrons

© Department of Chemistry, BUET

Dual nature of electrons
Sample questions:
 Mathematically show how Bohr’s postulate of quantization of orbital angular momentum in
the hydrogen atom is explained by de Broglie's hypothesis.
 Calculate the ratio of the de-Broglie wavelength of electron and proton moving with the
same speed.
 What will be the de Broglie wavelength of an electron travelling at an speed equal to 1% of
the speed of light?
 Show that the de-Broglie wavelength of an electron in the second Bohr's orbit is equal to
half of the circumference of 2nd Bohr’s orbit.

© Department of Chemistry, BUET

Schrödinger’s Quantum mechanical model
Key points:

 Electrons do not follow fixed paths

 They move randomly in areas of probability (orbitals)

 There are specific energies associated with each orbital

© Department of Chemistry, BUET

Quantum mechanical model
 The only quantity that can be known is the probability for an electron
to occupy a certain region around the nucleus.

 Schrödinger’s equation applied equally well to elements other than

hydrogen (unlike Bohr’s model).

 Bohr orbits were replaced with quantum-mechanical orbitals.

© Department of Chemistry, BUET

 Quantum mechanical model

“Anyone who can contemplate

quantum mechanics without getting
dizzy hasn’t understood it.”
--Niels Bohr

© Department of Chemistry, BUET

Quantum Mechanical Model - Schrödinger Wave Equation

 Ψ (psi) is a wave function, obtained by solving Schrödinger

wave equation; provides information about an electron in an
atom.
 Ψ2, gives the probability of finding the electron within a
region of space.

© Department of Chemistry, BUET

probability of density
Quantum Mechanical Model - Schrödinger Wave Equation

(A) The diagram shows the probability density for an electron in a hydrogen atom.
The region is marked off in shells about the nucleus.
(B) The graph shows the probability of finding the electron within shells at various
distances from the nucleus (radial probability).

© Department of Chemistry, BUET

Quantum mechanical model – probability density and radial probability
1s orbital 2s orbital 3s orbital

© Department of Chemistry, BUET

 Quantum mechanical model – radial and angular nodes
Nodal Surface of the 3p-orbital
07_107

X- axis

Yz plane

Radial Node: at a particular r Angular Node

© Department of Chemistry, BUET
Quantum mechanical model
 Each electron is described by Four Quantum numbers (QM)
Principal QM (n) :
• indicates the relative size and energy of atomic orbitals.
• n = 1, 2, 3,….

 This quantum number is the one on which the energy of an electron in an

atom primarily depends. The smaller the value of n, the lower the energy
and the smaller the orbital.

 Orbitals with the same value for n are said to be in the same shell.

 Shells are sometimes designated by uppercase letters:

Letter K L M N . . .
n 1 2 3 4

© Department of Chemistry, BUET

 Azimuthal QM/Subsidiary QM/Angular momentum QM (l)
 This quantum number distinguishes orbitals of a given n (shell) having different
shapes.

 It can have values from 0, 1, 2, 3, . . . to a maximum of (n – 1).

 For a given n, there will be n different values of l, or n types of subshells (denoted

by s, p, d or f).

 Orbitals with the same values for n and l are said to be in the same shell and
subshell.
An s orbital has spherical shape; a p orbital has two lobes; a
d orbital has four lobes; and an f orbital has eight lobes. n 1 2 3 4
l 0 1 2 3
Letter s p d f

Not every subshell type exists in every shell.

© Department of Chemistry, BUET
 Magnetic Quantum Number, m
 This quantum number distinguishes orbitals of a given n and l - that is, of a given
energy and shape but having different orientations.

 The magnetic quantum number depends on the value of l and can have any integer
value from –l to 0 to +l.

 For a given subshell, there will be (2l + 1) values

and therefore (2l + 1) orbitals.

© Department of Chemistry, BUET

Magnetic Quantum Number, m
When n = 1, l has only one value, 0; therefore, m has only one value, 0.

So, the first shell (n = 1) has one subshell, an s-subshell, 1s. That subshell, in
turn, has one orbital.

© Department of Chemistry, BUET

Magnetic Quantum Number, m
When n = 2, l has two values, 0 and 1.

When l = 0, ml has only one value, 0. So there is a 2s subshell with one

orbital.

When l = 1, ml has only three values, -1, 0, 1. So there is a 2p subshell with three
orbitals.

© Department of Chemistry, BUET

Magnetic Quantum Number, m
When n = 3, l has three values, 0, 1, and 2.

When l = 0, ml has only one value, 0. So there is a 3s subshell with one orbital.

When l = 1, ml has only three values, -1, 0, 1. So there is a 3p subshell with three
orbitals.
When l = 2, ml has only five values, -2, -1, 0, 1, 2. So there is a 3d subshell with
five orbitals

© Department of Chemistry, BUET

Magnetic Quantum Number, m
f orbitals

© Department of Chemistry, BUET

 Spin Quantum Number (s):
- defines the direction of spin on an axis of each electron (one axis,
therefore 2 spins possible)
Clockwise (+1/2)
Counterclockwise (-1/2)

© Department of Chemistry, BUET

Quantum Numbers and Atomic Orbitals

© Department of Chemistry, BUET

Subshell arrangement

© Department of Chemistry, BUET

  Aufbau Principle
 Electrons go into the subshell having the lowest possible energy.

___ ___ ___ ___ ___

1s 2s 2p

? ___ ___ ___ ___ ___

1s 2s 2p

© Department of Chemistry, BUET

Exceptions to the Aufbau Rule

Cr [Ar] 3 d44s2 Cu [Ar] 3 d94s2

However, the actual electron configuration, determined

experimentally, are:

Cr [Ar] 3d54s1 Cu [Ar] 3d104s1

© Department of Chemistry, BUET

 Pauli’s exclusion Principle
No two electrons in an atom have the same four quantum numbers

___ ___ __ __ __ ___ ___ __ __ __

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

© Department of Chemistry, BUET

 Hund’s Rule
• Every orbital in a subshell is singly occupied with one electron
before any one orbital is doubly occupied, and all electrons in singly
occupied orbitals have the same spin.

___ ___ __ __ __ ___ ___ __ __ __

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

© Department of Chemistry, BUET

Thank You

© Department of Chemistry, BUET