Chapter 7

Quantum Theory and the Electronic

Structure of Atoms
 Contents

7. 1 From Classical Physics to Quantum Theory

7. 3 Bohr’s Theory of the Hydrogen Atom
7. 6 Quantum Numbers
7. 7 Atomic Orbitals
7. 8 Electron Configurations
7. 9 The Building-Up (Aufbau) Principle
 7. 1 From Classical Physics to Quantum Theory

• Quantum theory: Enables us to predict and understand the

critical role of that electrons play in chemistry.
• Number of electrons found in a particular atom
• Energies associated with individual electrons
• Possible positions of the electrons.

• Properties of Waves
• Electromagnetic radiation
• Planck’s Quantum theory
Classical View of the Universe
• The physical universe has been classified as either
matter or energy
– Matter is anything that has mass and volume
– Energy is the entity that doesn’t have mass and volume but
it is needed to do work or produce a change.
• Matter is composed of particles and the properties
of those particles can be determined and we can
observe the properties
• Energy - not be composed of particles and the fact
common to all forms of energy is that it
travels/propagates in the form of waves
– Light is one of the forms of energy
4
 Electromagnetic Radiation

• In 1873 James Maxwell

proposed that the Waves have
two components
– Electrical field
– Magnetic field
• Technically, light is one type of a
more general form of energy
called electromagnetic radiation
• Electromagnetic radiation travels
in waves
5
 Electromagnetic Radiation
• Every wave has four characteristics that determine its
properties
– Wave speed (velocity)
– Wave height (amplitude)
– Wavelength
– Number of wave peaks that pass in a given time (frequency)

6
 Electromagnetic Waves
• Velocity = c = speed of light
– its constant! = 2.997925 x 108 m/s (m•sec-1)
in vacuum
– all types of light energy travel at the same
speed
Amplitude

• Amplitude = A = measure of the intensity

of the wave, “brightness”
– height of the wave
7
 Electromagnetic Waves
• Wavelength =  = distance between crests
– generally measured in nanometers (1 nm = 10-9 m)
– same distance for troughs or nodes

8
 Electromagnetic Waves
• Frequency = = how many peaks pass a point in a
second
– generally measured in Hertz (Hz),
– 1 Hz = 1 wave/sec = 1 sec-1
Low Frequency Wave

High Frequency Wave

9
 Properties of Waves: Summary

Wavelength () is the distance between identical points on successive

waves.
Amplitude is the vertical distance from the midline of a wave to the
peak or trough.
Frequency () is the number of waves that pass through a particular point
in 1 second (Hz = 1 cycle/s).
The speed (u) of the wave =  x  7.1
Electromagnetic Radiation

7.1
 Electromagnetic Radiation

Remember: Electromagnetic radiation is the emission and transmission

of energy in the form of electromagnetic waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

(will be given in exam)

All electromagnetic radiation

 x c or c/ -- remember this equation

7.1
 Practice Question

A photon has a frequency of 9.75 x 107 

Hz. Convert this frequency into
wavelength (nm). Does this frequency

fall in the visible region?
x=c
 = c/
 = 3.00 x 108 m/s / 9.75 x 107 s-1
 = 3.1 m
 = 3.1 x 109 nm
FM Radio wave
QBS Radio 97.5 FM!

You must review conversions of m to mm, to nm, etc. etc.

7.1
 Practice Exam Question
• Calculate the frequency of visible light having a wavelength
of 686 nm.
C = 3.00 x 10 m/s
8

4.37  1014 /s
 Quantum Theory: Particles of Light

• Scientists in the early 20th century showed

that electromagnetic radiation was
composed of particles - photons
– Max Planck and Albert Einstein
– Photons are particles of light energy
• Each wavelength of light has photons that
have a different amount of energy
– The longer the wavelength, the lower the
energy of the photons

15
 Quantum Theory: Particles of Light
Mystery #1, “Heated Solids Problem” Solved by Planck in 1900

When solids are heated, they emit electromagnetic radiation

over a wide range of wavelengths.

Radiant energy emitted by an object at a certain

temperature depends on its wavelength.

Energy (light) is emitted or

absorbed in discrete units
(quantum).

E = h x  remember this equation

Planck’s constant (h)
h = 6.63 x 10-34 J•s 16
 Planck’s law
E = h.ν
E is the energy of s single “photon” (a quantum of EM radiation)
Units: E(J) = h(J.s). ν(s-1)
h = 6.626x10 -34
J.s

h = The energy contained in a photon, which represents the smallest

possible 'packet' of energy in an electromagnetic wave.

Example: Calculate the energy of a photon of “yellow light” with λ = 580

nm (c = 3.00 x 108 m/s )
c = ν.λ ν = c/λ
Ephoton = h.ν = h.c/λ

Ephoton = 6.626x10-34 J.s x 3.00x108m/s / 5.80x10-7 m = 3.43x10-19 J

 Practice Exam Question
When copper is bombarded with high-energy electrons, X rays
are emitted. Calculate the energy (in joules) associated with
the photons if the wavelength of the X rays is 0.154 nm. h =
6.626x10-34 J.s. , c = 3.00 x 108 m/s

1.29 x 10 -15 J
 Practice Exam Question
When copper is bombarded with high-energy electrons, X rays
are emitted. Calculate the energy (in joules) associated with
the photons if the wavelength of the X rays is 0.154 nm.

E=hx
E = h x c /
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J

19
7. 3 Bohr’s Theory of the Hydrogen Atom

• Emission spectra
• Emission spectrum of hydrogen
 Light’s Relationship to Matter
• Atoms can acquire extra energy, but
they must eventually release it
• When atoms emit energy, it always is
released in the form of light
• However, atoms don’t emit all colors,
only very specific wavelengths
– in fact, the spectrum of wavelengths can
be used to identify the element

21
Emission Spectrum of Atoms
Emission Spectra
(line spectra_

Continuous
spectrum 22
Absorption Vs. Emission Spectrum

Absorption Spectrum Emission Spectrum

Absorption Spectrum

656.3 486.1 434.1 410.2

Emission Spectrum 23
7.3
Emission Spectrum of Hydrogen

Line Emission Spectrum of Hydrogen Atoms

7.3
 The Bohr Model of the Atom
• Based on the Emission spectral
characteristics observed, Neils Bohr
developed a model of the atom to explain
the 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

26
 The Bohr Model of the Atom
Electron Orbits
• In the Bohr Model, electrons travel in orbits
around the nucleus
• The farther the electron is from the nucleus the
more energy it has

27
 The Bohr Model of the Atom
Orbits and Energy
• Each orbit has a specific amount
of energy
• The energy of each orbit is
characterized by an integer - the
larger the integer, the more
energy an electron in that orbit
has and the farther it is from the
nucleus
– the integer, n, is called a
quantum number
28
 The Bohr Model of the Atom
Ground and Excited States
• In the Bohr Model of
hydrogen, the lowest amount
of energy hydrogen’s one
electron can have corresponds
to being in the n = 1 orbit –
ground state
• When the atom gains energy,
the electron leaps to a higher
energy orbit –excited state
• The atom is less stable in an
excited state, and so it will
release the extra energy and
return the electron to the 29
ground state
Bohr’s Model of Atom: Energy of Emitted Radiation

1. e- can only have

specific (quantized)
energy values
2. light is emitted as e- E = hn
moves from one energy
level to a lower energy
n4 n5
level n3
1 E = hn n2
En = -RH ( n2
)
n1
n (principal quantum number) = 1,2,3,…
RH (Rydberg constant) = 2.18 x 10-18J
RH will be given in exam
7.3
 Energy Associated with Emitted Photon

E = hn
Ephoton = E = Ef - Ei
n5
n4 1
n3 Ef = -RH ( 2 )
n2
nf
E = hn
1
n1 Ei = -RH ( 2 )
ni
1 1
E = RH( 2 )
ni n2f
7.3

7.3
 ni = 3 ni = 3

ni = 2 1 1
E = RH( )
nf = 2 n2i n2f

nnf f==11

7.3
Calculate the wavelength (in nm) of a photon
emitted by a hydrogen atom when its electron drops
from the n = 5 state to the n = 3 state.

1 1
ΔEatom = E = RH ( 2 )
ni n2f
ΔEatom = 2.18 x 10-18 J x (1/25 - 1/9)
Ephoton = -Eatom = 1.55 x 10-19 J
Ephoton = h x c /
 = h x c / Ephoton
 = 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
 = 1280 nm
7.3
 Practice Exam
• Calculate the wavelength, in nanometers, of the light emitted by a
hydrogen atom when its electron falls from the n = 7 to the n = 4
principal energy level. Recall that the energy levels of the H atom are
given by En = -2.18 x 10-18 J(1/n2) . h = 6.626x10-34 J.s. , c = 3.00 x
108 m/s

2.16 x 103 nm
 7. 6 Quantum Numbers
7. 7 Atomic Orbitals
• Quantum mechanical model
– The principle quantum number (n)
– The angular momentum quantum number (l)
– The magnetic quantum number (ml)
– The electron spin quantum number (ms)
• s, p, d and f orbitals
• The energies of orbitals
 The Bohr Model of the Atom
Success and Failure

• the mathematics of the Bohr Model very

accurately predicts the spectrum of hydrogen
• however its mathematics fails when applied
to multi-electron atoms
– it cannot account for electron-electron
interactions
• a better theory was needed

36
The Quantum-Mechanical Model of the Atom
• In 1926 Erwin Schrödinger
applied the mathematics of
probability and the ideas of
quantitization to the physics
equations that describe waves
• Resulting in an equation that
predicts the probability of finding
an electron with a particular
amount of energy at a particular
location in the atom

37
The Quantum-Mechanical Model Orbitals

• The result is a map of regions in the atom

that have a particular probability for finding
the electron
• An orbital is a region where we have a very
high probability of finding the electron
when it has a particular amount of energy
– generally set at 90 or 95%

38
 Schrodinger Wave Equation

• The Schrodinger equation describes both the

particle and wave nature of the e-
• Wave function () describes:
1. Energy of e- with a given 
2. Probability of finding e- in a volume of space

• Schrodinger’s equation can be used solve

probability of the electron distribution
exactly for the hydrogen atom.
• Must approximate its solution for multi-
electron systems. Electron Density

39
 The Quantum-Mechanical Model
Quantum Numbers

• In Schrödinger’s Wave
Equation, there are 3 integers,
called quantum numbers, that
quantize the energy
• The principal quantum
number, n, specifies the main
energy level for the orbital

40
 Quantum Numbers
 is a function of four numbers called
quantum numbers (n, l, ml, ms)
= fn(n, l, ml, ms)

Principal quantum number n

Distance of e- from the nucleus
n = 1, 2, 3, 4, ….

n=1 n=2 n=3

41
Where 90% of the
e- density is found
for the 1s orbital

7.6
 The Quantum-Mechanical Model
Quantum Numbers
• Each principal energy shell has one or more
subshells
– # of Subshells = Principle quantum number
• The quantum number that designates the subshell is
often given a letter
– s, p, d, f
• Each kind of sublevel has orbitals with a particular
shape
– The shape represents the probability map
• 90% probability of finding electron in that region

43
Shells & Subshells

44
 Quantum Numbers
= fn(n, l, ml, ms)
Angular momentum quantum number l
Shape of the “volume” of space that the e- occupies
For a given value of n, l = 0, 1, 2, 3, … n-1
l = 0 s orbital
n = 1, l = 0
l = 1 p orbital
n = 2, l = 0 or 1
l = 2 d orbital
n = 3, l = 0, 1, or 2
l = 3 f orbital

7.6
 Quantum Numbers

= fn(n, l, ml, ms)

magnetic quantum number ml

for a given value of l

ml = -l, …., 0, …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space

7.6
l = 0 (s orbitals)

l = 1 (p orbitals)

7.6
ml = -2, -1, 0, 1, or 2 5 orientations is space

l = 2 (d orbitals)

48
 ml = -1 ml = 0 ml = 1
Number of orbitals in p subshell = 3

ml = -2 ml = -1 ml = 0 ml = 1 ml = 2
Number of orbitals in d subsehell = 5 7.6
7.6
 Quantum Numbers

= fn(n, l, ml, ms)

Electron spin quantum number ms
ms = +½ or -½

ms = +½ ms = -½

7.6
 Quantum Numbers: Summary
= fn(n, l, ml, ms)

Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

How many electrons can an orbital hold?

If n, l, and ml are fixed, then ms = ½ or - ½

= (n, l, ml, ½) or= (n, l, ml, -½)

An orbital can hold 2 electrons 7.6
 The Energies of Orbitals
• The distribution of electrons into the various
energy shells, subshells and orbitals in an atom is
dependent on their energy levels

53
 7s 6d
6p 5f
5d
6s 4f
5p
4d
5s
4p
Energy

4s 3d
3p
3s
2p
2s

1s 54
 Order of orbitals (filling) in multi-electron atom

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

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
7.7
How many 2p orbitals are there in an atom?

n=2
If l = 1, then ml = -1, 0, or +1
2p
3 orbitals
l=1

How many electrons can be placed in the 3d

subshell?
n=3 If l = 2, then ml = -2, -1, 0, +1, or +2
3d 5 orbitals which can hold a total of 10 e-

l=2 7.6
 Practice Exam Question

• Electrons in an orbital with l = 2 are in a

d orbital
Practice Exam Question

B
 7. 8 Electron Configurations
7. 9 The Building-Up (Aufbau) Principle
 Quantum Numbers; Summary
Existence (and energy) of electron in atom is described
by its unique wave function .
Angular
Principal
quantum # or
quantum # or
shape of orbital
energy level
(s, p, d, f …..
= fn(n, l, ml, ms)
Magnetic Electron spin
quantum # or quantum #
special
ms = +1/2 or -
orientation of
orbital 1/2

Pauli exclusion principle - no two electrons in an atom

can have the same four quantum numbers.
7.6
 Electron Configurations
• The distribution of electrons into the various
energy shells and subshells in an atom in its
ground state is called its electron configuration
• Each energy shell and subshell can hold maximum
number of electrons as follows:
– s = 2, p = 6, d = 10, f = 14
• We place electrons in the energy shells and
subshells in order of energy, from low energy up
– Aufbau Principal

61
 7s 6
6p d 5f
5d
6s 4f
5p
4d
5s
4p
Energy

4s 3d
3p
3s
2p
2s

1s 62
Filling an Orbital with Electrons
Pauli Exclusion Principle
• Each orbital may have a maximum of 2
electrons
• Electrons spin on an axis
– Generating their own magnetic field
• When two electrons are in the same orbital,
they must have opposite spins
– So there magnetic fields will cancel

63
 Order of Subshell Filling
in Ground State Electron Configurations

Start by drawing a diagram

putting each energy shell on 1s
a row and listing the subshells, 2s 2p
(s, p, d, f), for that shell in
order of energy, (left-to-right) 3s 3p 3d
4s 4p 4d 4f
Next, draw arrows through
the diagonals, looping back 5s 5p 5d 5f
to the next diagonal 6s 6p 6d
each time
7s

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s 64
 Orbital Diagrams
• We often represent an orbital as a square or a line
and the electrons in that orbital as arrows
– The direction of the arrow represents the spin of the
electron

unoccupied orbital with orbital with

orbital 1 electron 2 electrons

65
 Electron Configurations
Electron configuration is how the electrons are
distributed among the various atomic orbitals in
an atom. number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H or
1s 1 1s1
7.8
The most stable arrangement of electrons
in subshells is the one with the greatest
number of parallel spins (Hund’s rule).

O
F
C
N
Ne97
6
810
electrons
electrons
electrons
Ne
C
N
O
F 1s 1s222s
2s2p2p3246
2 222 5

7.7
What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the

last (outermost) electron in Cl?

Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s

1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital

n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½

7.8
Practice Exam
 Core and Valence Electrons
• The electrons in all the subshells with the
highest principal energy shell are called the
valence electrons
• Electrons in lower energy shells are called
core electrons

Rb = 37 electrons = 1s22s22p63s23p64s23d104p65s1

• The behavior of an atom, both chemically

and physically, is dependent on the number
of valence electrons
70
 Ground State Electron Configuration

Rb = 37 electrons = 1s22s22p63s23p64s23d104p65s1
Abbreviated: [Kr] 5s1
• the highest principal energy shell of Rb that contains
electrons is the 5th, therefore Rb has 1 valence
electron and 36 core electrons
Kr = 36 electrons = 1s22s22p63s23p64s23d104p6
Abbreviated: [Ar] 4s23d104p6 or [Kr]
• The highest principal energy shell of Kr that contains
electrons is the 4th, therefore Kr has 8 valence
electrons and 28 core electrons
 Electrons Configurations and
the Periodic Table

 Elements in the same period (row) have valence electrons in

the same principal energy shell
 The number of valence electrons increases by one as you
progress across the period
 Elements in the same group (column) have the same number of
valence electrons and they are in the same kind of subshell.
 • Elements in the same column have similar chemical and physical
properties because their valence shell electron configuration is the
same
• The number of valence electrons for the main group elements is the
same as the group number
1 s 1
s2 p p p p p
1 2 3 4 5 s2
p6
2
3 d1
d2
d3
d 4
d 5
d 6
d 7
d 8
d 9
d10

4
5
6
7
f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14

73
 Electron Configuration from
the Periodic Table
• The inner electron configuration is the same as the
noble gas of the preceding period
• To get the outer electron configuration, from the
preceding noble gas, loop through the next period,
marking the subshells as you go, until you reach the
element
– the valence energy shell = the period number
– the d block is always one energy shell below the period
number and the f is two energy shells below

74
 Electron Configuration from
the Periodic Table
1A 8A
1 2A 3A 4A 5A 6A 7A
2 Ne
3 3s2 P
4 3p3
5
6
7

P = [Ne]3s23p3
P has 5 valence electrons 75
 Electron Configuration from
the Periodic Table
1A 8A
1 2A 3A 4A 5A 6A 7A
2
3 3d10 Ar
4 4s2 As
5 4p3
6
7

As = [Ar]4s23d104p3
As has 5 valence electrons
76
 Outermost subshell being filled with electrons
3d partially filled
e.g. Mn has 3d partially filled

4p partially filled

Orbital written in a particular row or region (i.e.

representative, transition elements, etc.) means those
orbitals are partially filled
7.8
 Practice Exam Question
• Which element has the following ground-state
electron configuration? [Kr]5s24d105p3

Sb
 ns2np6
ns1 Ground State Electron Configurations of the Elements

ns2np1

ns2np2
ns2np3

ns2np4
ns2np5
Exceptions:
ns2
Cr = 24 electrons = 1s22s22p63s23p64s13d5
Cu = 29 electrons = 1s22s22p63s23p64s13d10

d10
d1

d5

4f
5f

8.2
Classification of the Elements
Also classified as transition elements by some

Transition Elements =
‘B’ groups (all metals)

Bottom rows =
Main Group = Inner Transition
Elements = Rare
Representative Earth
Elements = ‘A’ Elements(Metals;
groups Really belong in
Period 6 & 7)

8.2
Magnetism and Unpaired Electrons

Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p 7.8
 Magnetism and Unpaired Electrons
• Is Mg paramagetic or diamagnetic?
• How many unpaired electrons are in this element?

Electron configuration of Magnesium

1s2 2s2 2p6 3s2

     
1s 2s 2p 3s 3p

Core electrons Valence electrons

 Practice Exam Questions

Q. How many valence electrons does a nitrogen atom have?

Q. Which ground-state atom has an electron configuration described

by the following orbital diagram?

A. phosphorus
B. nitrogen
C. arsenic
D. vanadium
E. none of these
5