The Quantum mechanical model of

the atom
SCH 100 Lesson 4

SCH 100 Lecture 4 1

 Recap Development of Atomic Models

Rutherford model
In the early twentieth century, Rutherford
Joseph John Thomson model showed that most of an atom's mass is
In the nineteenth century, Thomson described concentrated in a small, positively charged
the atom as a ball of positive charge containing region called the nucleus.
a number of electrons.

Bohr model Quantum mechanical model

After Rutherford's discovery, Bohr proposed Modern atomic theory described the
that electrons travel in definite orbits around electronic structure of the atom as the
the nucleus. probability of finding electrons within
certain regions of space.
Objectives
At the end of this Lecture you should be able to:
1) Explain the dual nature of matter and light
2) Describe qualitatively the Schrödinger
equation and the quantum numbers
3) Draw the shapes of atomic orbitals
4) Write electronic configurations of atoms

SCH 100 Lecture 4 3

Foundations of the Quantum
Theory
Prelude to Lesson 4
 Importance of electrons
• They determine the properties of atoms,
ions and molecules including the bonding
between or within them
• understanding of the electronic structures
of each species is vital in chemistry
• Best understood with reference to
quantum theory and wave mechanics.

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 Quantum Theory
• The need to explain some observations, e.g.,
– Black body radiation -
• At low temperatures, the radiation emitted by a hot
body is mainly of low energy and occurs in the infrared
region, but as the temperature increases, the radiation
becomes successively dull red, bright red and white.
– Photoelectric effect
• The ejection of electrons from certain metal surfaces
upon irradiation

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 Planck’s hypothesis
• Energy is absorbed or emitted only in discrete
amounts known as quanta and not continuously.
• Each quantum of energy is given by the equation
E = hn
Where n is the frequency of the radiation
and h is Planck’s constant = 6.626 x10-34 Js

The equation suggests:

• Energy associated with any radiation is proportional to its
frequency n
• Energy is quantized
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 Planck’s hypothesis

𝑐
𝐸 = ℎ𝜐 = ℎ
𝜆
• Notice that given either wavelength or
frequency we can calculate the energy. Given
the energy both the wavelength and
frequency are determined.

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 The Photoelectric Effect
• The ejection of electrons from certain metal
surfaces when irradiated with high energy
electromagnetic radiation like ultraviolet
light.
• First recognized by Heinrick Hertz in 1887

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 Characteristics of the Photoelectric Effect

1. No electrons ejected unless frequency

exceeds a threshold frequency value, νo
characteristic of each metal.
2. The kinetic energy of the emitted
electrons is linearly dependent on the
frequency of the incident light but is
independent of its intensity
Classical physics could not explain these observations
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Explanation of the PE
• Einstein (1905) used Planck’s quantization
theory to explain PE.

• He proposed that radiation consisted of

particles or corpuscles (now known as photons
after GN Lewis).

• Wave-particle duality of matter

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The Wave-particle Duality of matter

• Refers to the possibility of matter possessing both

the wave and particle (or particulate) natures
under appropriate conditions.
• Einstein has shown that radiation has both wave
and particle nature from the Photoelectric effect.
• Is it possible that particles can also have wave
nature?

SCH 100 Lecture 4 13

 The De Broglie hypothesis
All matter, not just light, has a wave-like nature.
• The wavelength and momentum of such matter are
related by the equation :
h

mv
• Proved accurate in 1927 by acceleration of electrons
onto a barrier.
• He won Nobel prize of 1929.
SCH 100 Lecture 4 14
Proof of De Broglie Hypothesis
• In 1927 C. J. Davisson and L. H. Germer
showed that the electron beam was scattered
by the surface atoms on the nickel at the exact
angles predicted for the diffraction of x-rays
according to Bragg's formula, with a
wavelength given by the de Broglie equation,
λ = h / mv.

SCH 100 Lecture 4 15

• Again in 1927, G. P. Thomson reported his
experiments, in which a beam of energetic
electrons was diffracted by a thin foil. Thomson
found patterns that resembled the x-ray patterns
made with powdered (polycrystalline) samples.
• This kind of diffraction, by many randomly
oriented crystalline grains, produces rings. If the
wavelength of the electrons is changed by
changing their incident energy, the diameters of
the diffraction rings change proportionally, as
expected from Bragg's equation.

SCH 100 Lecture 4 16

 Electron Diffraction Experiment

Source:
http://dev.physicslab.org/Document.aspx?doctype=3&filename=AtomicNuclear_DavissonGer
mer.xml
SCH 100 Lecture 4 17
 Heisenberg’s Uncertainty Principle
• It is impossible to simultaneously know
both the position and momentum of an
object as small as an electron.
• Mathematically; h
xp 
Where 4
Δx = error (or uncertainty) in position
Δp = error (or uncertainty) in momentum

http://www.aip.org/history/heisenberg/p08.htm
SCH 100 Lecture 4 18
 Heisenberg’s Uncertainty Principle
• It did away with Bohr’s ideas of electrons being
in definite orbits where the position and velocity
are known exactly.
– These were replaced by the probability of finding
and electron in a particular position or volume of
space.
– Orbits were replaced with orbitals
– Electron particle was replaced with electron cloud.
Thus, an orbital is a volume in space where 95%
of the electron cloud is expected to be found.
SCH 100 Lecture 4 19
 Heisenberg’s Uncertainty Principle
• It demonstrated the need to find a microscopic
or atomic equation equivalent to the Newton’s
second law of motion which would have to
include the Planck postulate E = hn as well as
the de Broglie wave postulate, λ = h/mv.

• This was developed by Erwin Schrödinger in

1926.

SCH 100 Lecture 4 20

The Time Independent Schrodinger Equation
 2ψ  2ψ  2ψ 8π 2 m
    E  V ψ  0
x 2 y 2 z 2
ĤΨ = EΨ h2

SCH 100 Lecture 4 21

 Hamiltonian operator, Ĥ
• Ĥ is an operator used to determine the total
energy of a given system
Ĥ = kinetic energy(T) + potential energy(V)
• The kinetic operator, T, is a second derivative of
position and takes the form that follows the
coordinate system (x, y, z or r, θ, φ)
• The potential operator, V, is a function of
position and takes the form that follows the
system description (whether potential is zero,
etc).
SCH 100 Lecture 4 22
The Time Independent Schrodinger Equation

2 2
 ψ  ψ  ψ 2 2
8π m
2

2

2

2
 E  V ψ
x y z h
Where
(psi) = wave function
m = mass of the electron
E = total energy of the electron
V = potential energy of the electron
(E-V) = Kinetic energy of the electron
SCH 100 Lecture 4 23
Solving the Schrodinger Equation
• Gives the
–Eigen functions, n(x,y,z) and
–the Eigen values, En.
• Each Eigen function n(x,y,z) is associated
with an atomic orbital.

SCH 100 Lecture 4 24

Atomic Orbitals

• An atomic orbital is a mathematical

function that describes the wave-like
behavior of either one electron or a pair of
electrons in an atom.

• Atomic orbital -a boundary surface which

encloses 95 % of the electron density for a
particular ψ.
SCH 100 Lecture 4 25
Quantum numbers
• Each ψ is written in terms of three quantum
numbers
– n, principal quantum number
– l , orbital angular momentum quantum number
a.k.a azimuthal quantum number
– ml , magnetic quantum number
• These characterize every solution of the
Schrödinger equation.

SCH 100 Lecture 4 26

 Quantum numbers
• They are related as follows:
1. n is the principal quantum number,
• It determines size and energy of
an orbital
• n = 1, 2, 3, ……, ∞.

SCH 100 Lecture 4 27

 Quantum numbers
2. l is azimuthal or orbital angular
momentum quantum number,
• It determines shape
• = 0, 1, 2, .., (n – 1), for each value of n.
3. ml magnetic quantum number,
• Describes the orientation in space
• = 0, ±1, ±2, ….., ±l for each value of l.

SCH 100 Lecture 4 28

 Orbital angular momentum quantum
numbers and atomic orbitals
• From spectroscopy the ψ are given letter notations
depending on the value of l as follows:
0 1 2 3 4 5 etc
l
Notation s p d f g h
s – sharp, p - principal, d-diffuse, f-fundamental

SCH 100 Lecture 4 29

 Atomic orbitals
Subshell No of Total no of
n l designation ml orbitals in orbitals in
subshell shell
1 0 1s 0 1 1
2 0 2s 0 1
1 2p -1, 0, 1 3 4
0 3s 0 1
3 1 3p -1, 0, 1 3 9
2 3d -2, -1, 0, 1, 2 5
4 0 4s 0 1
1 4p -1, 0, 1 3 16
2 4d -2, -1, 0, 1, 2 5
3 4f -3,-2,-1,0,1,2,3 7
SCH 100 Lecture 4 30
• Number of subshells in a shell number n = n
• For each l value, there are 2l+1 allowed ml
values
• Total number of orbitals in a shell = n2

SCH 100 Lecture 4 31

 Spin Quantum Number ms
• Since electron behaves as if it is spinning about an
axis, a spin quantum number ms is also required to
uniquely described an electron in an atomic orbital.
• ms = +½ or -½
Shapes of the orbitals
• Atomic orbital -a boundary surface
which encloses 95 % of the electron
density for a particular ψ.
• Pictorial representation
– by boundary surface diagrams
– electron density contour plots.

SCH 100 Lecture 4 33

Boundary surface diagrams
s orbital is spherical.

SCH 100 Lecture 4 34

Boundary surface diagrams

SCH 100 Lecture 4 35

p orbitals together

SCH 100 Lecture 4 36

d-orbitals

SCH 100 Lecture 4 37

 Boundary surface diagrams

SCH 100 Lecture 4

38
SCH 100 Lecture 4 39
The f-orbitals

SCH 200 Lecture 3 40

 Many-electron atoms
• A given electron moves under the
influence of the nucleus and repulsion
of other electrons.
• The influence of electrons on each
other in an atom can be envisaged in
two interrelated phenomena:
–The screening effect
–Penetration effect
SCH 100 Lecture 4 41
The Screening effect
• Consists of a reduction of the nuclear
attraction on an electron due to the
presence of other electrons nearer the
nucleus than the electron under
observation.

SCH 100 Lecture 4 42

 The Screening effect
• The other electrons lower the full charge
of the nucleus from Z to Z* - the effective
nuclear charge. Thus, the electron is
said to be screened. Z* = Z-S
• Screening increases with number of e-
shells

SCH 100 Lecture 4 43

 Penetration effect
• Arises from the wave nature of the electron
(quantum mechanics).
• Some of the time even outermost electrons
are in the region near the nucleus where
screening is minimum.
– Thus they can be said to penetrate through the inner
electron shells to the nucleus.

SCH 100 Lecture 4 44

 Penetration effect
• For a given n value, penetration varies
as follows: s>p>d>f.
• Energy of orbitals : s<p<d<f

SCH 100 Lecture 4 45

• No Screening & penetration effects,
• All orbitals in a shell are degenerate,
E.g. in shell 4 : 4s = 4p = 4d = 4f

SCH 100 Lecture 4 46

• Screening & penetration effects
high
• Energy of orbitals: s<p<d<f
SCH 100 Lecture 4 47
 The Electron Spin
N S

Anticlockwise Clockwise
N
S
ms = +½ ms = -½
SCH 100 Lecture 4 49
 The Electron Spin
• The electron behaves as if it spinning
about an axis through its centre.
• The electron spin generates a
magnetic field, the direction of which
depends on the direction of spin.

SCH 100 Lecture 4 50

 The Electron Spin
• The two directions of spin corresponds to
the two possible values for the spin
quantum number, ms = ±½.
• Otto Stern and Walter Gerlach (1921)
demonstrated experimentally that a beam
of gaseous silver atoms would be
separated into two when passed through
an inhomogeneous magnetic field.
SCH 100 Lecture 4 51
Recap-Penetration effect
• For a given n value, penetration
varies as follows: s>p>d>f.
• Energy of orbitals : s<p<d<f

SCH 100 Lecture 4 55

 Presentation of electrons

• Electron configurations
–Long notation
–Short/noble gas notation
• The periodic Table

SCH 100 Lecture 4 56

Representing Electrons in atoms

There are 3 types of electron diagrams:

• An orbital filling diagram, and
• A Lewis or electron dot diagram.
• An electron configuration,

SCH 100 Lecture 4 57

 Orbital filling diagram
• Uses a box or line to represent each
atomic orbital. Under each box or line is
the orbital designation.
• Arrows are used to show 1 or 2 electrons
and their spin. For example, 2 electrons in
1s orbital


2
or 
1s SCH 100 Lecture 4
1s 2
58
 Lewis or electron dot diagram
• Shows a series of 1-8 dots in pairs around
the element symbol.
– Only valence (the highest numbered PEL) electrons in
are shown.
– Example, the noble gas neon should be;

SCH 100 Lecture 4 59

 Question

• Write the Lewis dot diagram for the

following atoms:
Li, Be, B, Al, P, F

SCH 100 Lecture 4 60

 Electron configuration
• Shows PEL, sublevel, and how many
electrons are in each sublevel. E.g. the
four electrons in a 3p subshell.

SCH 100 Lecture 4 61

 Examples

Lewis dot and Electron

configuration diagrams for Na and
Cr:
Na [1s 2s 2p ]3s
2 2 6 1

Cr [1s 2s 2p 3s 3p ]3d 4s
2 2 6 2 6 5 1

SCH 100 Lecture 4 62

Questions to answer
• What determines the orbitals in
which electrons reside?
• How do the electrons in a many-
electron atom populate the available
orbitals?

SCH 100 Lecture 4 63

Electron Configurations
• The way in which electrons are distributed
among the various orbitals of an atom.
• Arrangement of electrons in atoms follow
some order governed by the following
laws:
1. Aufbau Principle (Build up principle)
Lowest energy orbitals are filled with
electrons first, i.e. 1s, 2s, 2p, 3s, 3p, etc.

SCH 100 Lecture 4 64

2. Pauli Exclusion principle
• No two electrons in an atom or
molecule can have all four quantum
numbers the same .
– Only two electrons may occupy an orbital.
– Electrons in the same orbital must have
opposite spins
E.g.
Unpaired electron
H 1s1
Paired electrons or
He 1s2 electron spin
Li 1s22s1
Be 1s22s2
SCH 100 Lecture 4 65
Consider the three possible ways
of placing two electrons in the 1s:

↑↑ ↓↓ ↑↓
1s 2 1s 2 1s 2

(a) (b) (c)

SCH 100 Lecture 4 66
3. Hund's maximum multiplicity rule

• If two or more degenerate orbitals are

available, electrons go into each
degenerate orbital with parallel spins until
the orbitals are half-filled before pairing
starts.
e.g. in N, 1s22s22px1 2py12pz1 ≡ 1s22s22p3

SCH 100 Lecture 4 67

Order of filling orbitals

SCH 100 Lecture 4 68

 Order of filling orbitals
1s The Aufbau Diagram
• It shows the order in which
2s 2p energy sublevels fill with
electrons.
3s 3p 3d
• After element number 18,
Ar, 4s orbitals are filled
4s 4p 4d 4f
before 3d. 4s is of lower
energy than 3d and fills first
5s 5p 5d 5f

6s 6p 6d
• Similarly 5s fills before 4d.

7s

SCH 100 Lecture 4 69

SCH 100 Lecture 4 70
Examples
1H 1s1
2He 1s2
3Li 1s2 2s1 = [He]2s1 Try
12Mg
4Be 1s2 2s2 = [He]2s2 13Al
5B 1s2 2s22p1 = [He]2s22p1 18Ar
6C 1s2 2s22p2 = [He]2s22p2 19K
10Ne 1s22s22p6 = [He]2s22p6 20Ca
11Na 1s22s22p63s1 = [Ne]3s1 21Sc

SCH 100 Lecture 4 71

Exceptions to the filling order
• There are many exceptions to the
filling order rules.
• Most are unpredictable, except
these.
–The d-sublevel has 5 orbitals.
–There seems to be something
energetically stable about having that
sublevel exactly half full (d5) or
completely full (d10).
SCH 100 Lecture 4 72
 Order of filling orbitals
1s The Aufbau Diagram
• It shows the order in which
2s 2p energy sublevels fill with
electrons.
3s 3p 3d
• After element number 18,
Ar, 4s orbitals are filled
4s 4p 4d 4f
before 3d. 4s is of lower
energy than 3d and fills first
5s 5p 5d 5f

6s 6p 6d
• Similarly 5s fills before 4d.

7s

SCH 100 Lecture 4 73

Exceptions to the filling order
Examples:
• Chromium is element 24 and copper is 29.

Element Predicted e- Actual e-

configuration configuration
Cr [Ar] 3d44s2 [Ar] 3d54s1
Cu [Ar] 3d94s2 [Ar] 3d104s1

SCH 100 Lecture 4 74

 Exercise
• Write the electronic configurations of elements
with atomic numbers 1 to 36
• Work out the maximum number of electrons for n
= 4.
• Write the four quantum numbers for a 3p
electron.

http://www.chem.ox.ac.uk/vrchemistry/
SCH 100 Lecture 4 75