CHAPTER 3

Atomic
and
Electronic structure
Electronic
structure
 Background: basic structure
• Sub-atomic particles include: Protons (p+),
neutrons (n) and electrons (e–)
• n: neutral, massive, in nucleus,
• e–: -ve, small mass, orbits,
• p+: +ve, massive, in nucleus
• Nucleus is small compared to size of atom

e– p+ n°
n° p+

Helium atom is
e– shown
 Background: basic structure
• Previous slide was a single atom
• Let’s look at a compound:

Cl Na

• Notice that the nuclei are far apart

• Only the outer regions come in close contact
• In other words, it’s the electrons that are
important in bond formation
• 1930s; Rutherford had proposed that
electron is negatively charge that fill the
volume of the atom (orbit).
– Argued: the speed of the movement and
distance from the nuclei. This 2 important
information is needed in order to explain the
orbit movement. Too fast: out of orbit; too
slow: e- will attract to the nuclei.
To overcome this problem, Neils Bohr come out
with new theory (Bohr Theory)
 Background
• Rutherfords model (1930s) is in trouble: an
“accelerated charge” should fall into nucleus

• Bohr revised Rutherford’s model to explain the

existance of line spectra for elements…
 electron orbits
• Bohr suggests that electrons can only exist in
certain orbits
 line spectra
• Line spectrum result from the release of
photons as electrons fall back to lower orbit
• The basic clue to the electronic structures of
atoms comes from the study of the light
emmited when atoms of the elements are
excited, or energized.
• To learn about this, however, you must first
learn a little about light itself.
• As we know energy can be transferred as
light energy (important form of energy in
chemistry)
• B’coz many chemical systems emit visible
light as they react.
More properly called
electromagnetic energy
Combustion

Cyalume light stick

A lightning bug
• Electromagnetic energy: energy carried
through space or matter by means of
wavelike oscillations (systematic
fluctuations in the intensities of very tiny
electrical and magnetic forces).

• Electromagnetic radiation/ light wave:

changes rhythmically with time, and the
successive series of oscillation that travel
through space.
 Light as a wave
• To understand the evidence that led Bohr to
his conclusion we must understand
something about the nature of light…
• light is a type of EM energy and has wave
properties.
• Wavelength and frequency are related by
 x  = c = 3.00 x 108 m/s
• Frequency (or wavelength) determines the
type of radiation.
 c



c y = the max. height of the wave above centre line or the max. depth


below
λ = wavelength; the distance between the tops of the two successive crest


(or the bottom of two troughs); unit in meter
ν= frequency; the number of crest or troughs that pass through a given
point per unit of time; unit hertz (Hz)
c = the speed of electromagnetic radiation in a vacuum
(speed of light) 3.00 X 108 ms-1
Calculating frequency from wavelength

• What is the frequency in hertz of yellow

light that has a wavelength of 625 nm?
• Solution:
 ν = 3.00 X 108 ms-1
625 X 10-9 m
= 4.80 X 1014 s-1
= 4.80 X 1014 Hz
 The electromagnetic spectrum


 Electromagnetic radiation comes in a broad range of frequencies
called the electromagnetic spectrum.

 Most of the time, you are bombarded with electromagnetic

radiations from all portion of the EM spectrum.
 Radio & TV signals pass through you
 You feel infrared radiation when you sense the warmth of a
radiator
 X rays and gamma rays fall on you from space
 Light from a lamp reflects into your eyes from the page
you’re reading
 our eyes are able to sense only a very narrow band of
wavelength ranging from about 400 nm to 700 nm
 this band is called the visible spectrum
 The speed of EM waves
• Which is a radio wave, which is a visible
wave (not drawn to relative scale)
• Observe what happens as they move
through space (at same speed of c)

Visual

Radio
 The speed of EM waves
• Which is a radio wave?, which is a visible
wave? (not drawn to relative scale)
• Observe what happens as they move
through space (at same speed of c)

Visual

Radio
 The speed of EM waves
• Which is a radio wave, which is a visible
wave (not drawn to relative scale)
• Observe what happens as they move
through space (at same speed of c)

Visual 6 Hz

Radio 3 Hz

• The longer the wavelength, the smaller the

frequency has to be to keep c constant
 The speed of EM waves
Q - Which of the following has the higher
frequency ?:
a) visible light or UV (choose one)
b) X-rays or radio waves (choose one)

Q - Which of the following pairs has the longer

wavelength:
c) Infrared or Ultraviolet (choose one)
d) Gamma rays or Radio waves (choose one)
 The energy of EM radiation
• In 1900 a German physicist named Max Planck
(1858 – 1974) launched one of the greatest
upheavals in the history of science when he
proposed that electromagnetic radiation is emitted
only in tiny packets or quanta of energy that were
later called photons.

• Planck proposed, and Albert Einstein (1879-2955)

confirmed, that the energy of a photon of
electromagnetic radiation is proportional to its
frequency.
 Planck’s Constant
Transfer of energy is quantized, and can only
occur in discrete units, called quanta.

hc
E = h =

E = change in energy, in J
h = Planck’s constant, 6.626  1034 J s
ν = frequency, in s1
 = wavelength, in m
E  hv
c
 

hc
E 

 How fast does a wave move?
• In the vacuum of space, wave speed is 300,000
km/s or 3 x 108 m/s
• We use C to stand for speed
• Isn’t 3 x 108 m/s the speed of light?
• Why, yes it is!
• This is a very strong piece of evidence that light
and electromagnetic radiation are the same thing.
• When not in space, the speed of the wave depends
on what it’s traveling through.
 What’s the difference between
waves and particles?
• It’s not clear.
• We do know that light can behave as a particle,
called a photon, whose energy depends on
frequency.
• Photons are kind of like lumps of energy, we can
also call them quanta.
• They are really the particles that make up our
wave. Since they are particles- and they move in a
wave- I guess they move as both a particle and a
wave!
• All particles can behave like a wave.
 What are photons used for?
• When an electron wants to go down an energy
level, it uses a photon (an energy lump)
• When the electron wants to go up an energy level-
it emits photons.
• It’s those emitted photons that make up the
electromagnetic wave.
• The number of vibrations it is moving per second
will tell us what KIND of wave it is!
 Atomic Spectrum of Hydrogen

• Continuous spectrum: Contains all the

wavelengths of light.

• Line (discrete) spectrum: Contains only

some of the wavelengths of light.
(a) A continuous
spectrum containing
all wavelengths of
visible light.

(b) The hydrogen

line spectrum
contains only a few
discrete
wavelengths.
• In 1885, J. J. Balmer found an 2
equation that was able to give  n
the wavelength of the lines in 2
the visible portion of the n 1
spectrum.

• This was soon extended to a

more general equation by
Robert rydberg which called 1  1 1 
   
Rydberg equation (that could  RH  2 2 
be used to calculate the  n1 n 2 
wavelength of all the spectral
lines of hyrogen).
 1  1 1 
 RH  2  2 
  
 n1 n 2 

RH = is a constant; 109 678 cm-1

2 2
n1 & n2 = are variables whose values are whole numbers that
range from 1 to ∞; n2 > n1
Lowest energy state; stable
The Bohr Model of the Hydrogen Atom
• Bohr successfully accounted for the Rydberg
equation by using his model.
• Bohr likened the electron moving around the
nucleus to a planet circling the sun.
• He suggested that the electron moves around
the nucleus along fixed paths, or orbits which
means that each of the orbits is identified by
its value of n (quantum number).
 b
E 
n
2
Bohr’ s equation:
E  E  El
h

 b  b
  2 
   2

 n h   nl  E: energy of the electron
 1 1 
 b 2 


n n b: constant; 2.18 X 10-18 J
n h 
2 h l
 nl

E 
hc Eh: higher initial energy


1
 hc  
El: lower final energy
 

 1 1  1 nh: initial quantum number of

b 2    hc  

n h   the electron
2
 nl

1 b  1  1 

  
hc  n 2
nl: final quantum number
  n h 
2
 l

1  1 1 
     
R  2
  n h 
H 2
 nl
 Wave properties of matter and wave
mechanics
• Light waves are characterized by their
wavelength and their frequencies.
• The same is true of matter waves.
• De Broglie suggested that the wavelength of a
matter wave, λ, is given by the equation:

h

mv
h: planck’s constant
m: particle’s mass Louis de Broglie
v: velocity (1892-1987)
• From the equation, the heavy objects have extremely
short wavelengths.

• But tiny particles with very small masses have much

longer wavelengths, so their wave properties become
an important part of their overall behavior.

• Perhaps by now you’ve begun to wonder if there is any

way to prove that matter has wave properties.

• These properties can be demonstrated by a

phenomenon that you have probably witnessed.

• For example: raindrops fall on a quiet pond

 Examples:

1) Calculate the wavelength of a band on your

FM radio with a frequency of 93.8 Hz.
Solution:
  c/v
_
3.0 𝑥 108 𝑚 𝑠 1
= _
93.8 𝑠 1

= 3.2 x 106 m
2) Calculate the wavelength of the light emitted
for an electron transition from the sixth to the
third orbit of the hydrogen atom.
Solution:

n1 < n2

= 1.097 x 107 m-1 [1/32 -1/62]

  1.09 x 10-6 m
3) Calculate the energy emitted when an
electron drops from the energy level n =7 to
n=3.

n1 < n2

Why use 2.18 x

∆E = 2.18 x 10-18 J [1/32 – 1/72] 10-18 J ?
Please refer to
∆E = 1.98 x 10-19 J slide 33 (Bohr’ s
equation)
4) What is the speed that an electron be
accelerated to, in order to have a wavelength of
180 nm? (Given; mass of electron is 9.11 x 10-31 kg
[ 1 J = 1 kg m2 s-2])

Solution:
  h / mv
V=h/m
 6.63 x 10-34 kg m2 s-2 s
(9.11 x 10-31 kg) (180 x 10-9 m)
= 4043 m s-1
Quantum Numbers
 Quantum Numbers
According to Heisenberg’s Uncertainty
Principle, it is not possible to give the exact
position of an electron and its energy at
the same time.
But the probability of finding an electron
in an orbital of given energy can be
determined.
The Three Physicists
Louie de Broglie
Erwin Schrodinger
Werner Karl Heisenberg

Quantum Mechanical Model

 The Quantum Mechanical Model

• An orbital:
– describes a specific distribution of electron density in
space
– has a characteristic energy
– has a characteristic shape
– is described by three quantum numbers: n, l, ml
– can hold a maximum of 2 electrons

• Note: A fourth quantum number (ms) is needed

to describe each electron in an orbital
 The 4 Quantum Numbers
Principal Quantum Number, n
Azimuthal Quantum Number, l
Magnetic Quantum Number, ml
Spin Quantum Number, ms
 The Principle Quantum Number, n
• The quantum number, n is called the principal
quantum number.
• All orbitals that have the same value of n are said
to be in the same shell.
• Range: n = 1 to n = ∞
• n=1 first shell
• n=2 second shell
• Sometimes identified by letters (with no
significant reason) beginning with K for the first
shell.
• n is related to the size of the electron wave
(how far the wave effectively extend from the
nucleus).
• n; electron’s average distance from the
nucleus.
• n also related to the energy of the orbital.
• n; Eorbital

• Bohr theory failed for atom other than

hydrogen b’coz when the atom has more than
one electron, different orbitals with the same
value of n can have different energy.
The Secondary Quantum Number, l
• Also called the azimuthal quantum number /
also know as angular momentum quantum
number
• l, divides the shells into smaller group of orbitals
called subshells.
• The value of n determines which values of l are
allowed.
• Range: l = 0 to l = (n-1)
• Example:
 n = 1; (n-1) = 0, so the only value of l that’s allowed is
zero.
 Azimuthal Quantum Number
l Subshell Total orbitals Orbital
(2l + 1) Shape
0 sharp - s 1 spherical

1 principal - p 3 dumbbell-
shaped
2 diffused - d 5 cloverleaf

3 fundamental - f 7 too
complex
 value of n value of l Kind of Subshell
1 0 1s
2 0, 1 2 s, 2p
3 0, 1, 2 3 s, 3 p, 3 d
4 0, 1, 2, 3 4s, 4p, 4d, 4f
n 0, 1, 2, … (n – 1)

l 0 1 2 3

Sign of orbital s p d f

Total orbitals 1 3 5 7
2l + 1
 Summary: p orbitals and d orbitals
p orbitals look like
a dumbell with 3
orientations: px,
py, pz (“p sub z”).
Four of the d orbitals resemble two dumbells in a
clover shape. The last d orbital resembles a p
orbital with a donut wrapped around the middle.
 The Quantum Mechanical Model
• s-orbital:
– spherical probability region

1s
– found in all shells of an atom
2s
– the size of the s-orbital increases with
increasing n 3s
• as n increases an electron
has a greater probability of being found far
from the nucleus
 The Quantum Mechanical Model

• p-orbital
– Three p orbitals in all shells when n > 2
– Figure 8 or dumbbell shaped
• same size and energy within same shell
• different spatial orientation
 The Quantum Mechanical Model
• d-orbitals
– five d orbitals are present in each shell where n > 3
– same energy within same shell
– different shapes
– different orientation
in space
 The Quantum Mechanical Model

• f-orbitals

– When n > 4, there are seven equivalent f orbitals

in each shell.

– Complicated shapes
 Magnetic Quantum Number, ml

describes the orientation in space of the orbital

integral values between l and -l
• If l = 1, then ml = 1, 0, -1

ml = -1 ml = 0 ml = 1
 Spin Quantum Number, ms

• The first three quantum numbers (n, l, ml) describe

an individual orbital.

• A fourth quantum number is used to describe each

electron found in an orbital.

• Electron spin quantum number (ms)

ms = + 1/2 ( ) or

ms = -1/2 ( )
value value of l Kind of Subshell Total Maximum
of Orbitals electron
n n2 population of a
shell
2n2

1 0 1s 1 2

2 0, 1 2s, 2p 4 8

3 0, 1, 2 3s, 3p, 3d 9 18

4 0, 1, 2, 3 4s, 4p, 4d, 4f 16 32

n 0, 1, 2, … (n – 1)
 The Quantum Mechanical Model

• One important factor that influences the

distribution of electrons is the phenomenon
known as electron spin.
• Electron spin: a property of
electrons that make it behave
as if it were a tiny magnet
spinning on its axis.
 Orbital Diagrams

• The orbitals in an atom can be depicted using an

orbital diagram that indicates the relative
energies of the orbitals.

• For a hydrogen atom (or an ion containing only 1

electron), all of the orbitals with the same
principal quantum number are degenerate
– have the same energy.
 Orbital Diagrams

3s 3p 3d
n=3

n=2
Energy 2s 2p

n=1

1s
 Orbital Diagrams
orbital
3s 3p 3d
n=3

subshell
3s 3p 3d
n=3

shell

3s 3p 3d
n=3
 The Quantum Mechanical Model

• The collection of orbitals with the same value of n

is called an electron shell.

– All orbitals that have n = 3 are in the third shell.

• The set of orbitals that have the same n and l

values is called a subshell.

– All orbitals with n = 3 and l = 2 are called the 3d

orbitals and are located in the 3d subshell.
 Orbital Diagrams

• For a hydrogen atom or an ion containing only

one electron, the energy of a subshell
depends only on its principal quantum
number.
– i.e. 3s, 3p, and 3d subshells all have the same
energy

• This is not true for atoms or ions that have

more than one electron.
 4p
3d

4s

3p Orbital Diagrams
for
3s Many Electron
Atoms
2p
Energy
2s

1s
 Orbital Diagrams
• In atoms with more than one electron,
electron-electron repulsion causes different
subshells within the same shell to have
different energies.
– Within the same shell: s < p < d < f

– Note that there is overlap in the subshell energies:

• 4s is lower energy than 3d
 Orbital Diagrams

Diagonal Diagram:
1s
2s 2p a guide used to
3s 3p 3d determine the relative
4s 4p 4d 4f energies of subshells in
multi-electron atoms
5s 5p 5d 5f
6s 6p 6d 6f
7s 7p 7d 7f
 Orbital Diagrams
• How do we know where the electrons in an atom
reside?
– What is the energy of each of the electrons? (i.e. which
orbitals are occupied first?)
• Aufbau principle
• Hund’s rule

– How many electrons can occupy each orbital?

• Pauli Exclusion Principle
 Orbital Diagrams
• Pauli Exclusion Principle: No two electrons in
an atom can have the same set of four
quantum numbers n, l, ml, and ms.

• In order to put more than one electron in an

orbital, electrons must have different values of
ms .
– i.e. they must have different spins
– Maximum of 2 electrons per orbital
 Orbital Diagrams
• Distributing electrons in orbitals:
– Electrons are placed in the lowest energy orbital
available (aufbau principle)

– Not more than 2 electrons can occupy the same

orbital (Pauli Exclusion Principle).
• Two electrons can occupy the same orbital only if their
spins are paired (i.e. opposite)
 Orbital Diagrams
• Distributing electrons in orbitals (cont):
– If more than one orbital in a subshell is available,
electrons will fill empty orbitals in the subshell
first. (Hund’s Rule)
• Keep electrons unpaired as long as an empty
orbital with the same energy is available.

– Unpaired electrons: electrons that are alone in an

orbital; not accompanied by another electron of
opposite spin.
 Questions:
1. a) State the number of sub shells in the third shell
b) Name each of these sub shells
c) How many orbitals are in these sub shells?
Solution:
a) n =3 l = 0,1,2 ; number of subshells is 3
b) n = 3
l = 0  3s
l = 1  3p
I = 2  3d

c) 3s  1 Orbitals
3 p  3 orbitals
3 d  5 orbitals
So total = 9 orbitals
 Hund’s rule
• The number of electrons in the 3d orbitals of
the atom with Z=24 is,
• A: 3
• B: 4
• C: 5
• D: 6

• Answer is C: 5 (by considering hund’s rule)