 6.1.

Electromagnetic radiation
 6.2. Quantization: Planck, Einstein, Energy and Photons

 6.3. Atomic line spectra and Niels Bohr

 6.4. Particle-wave duality: Prelude to quantum mechanics

 6.5. The modern view of electronic structure: Wave or quantum

mechanics
 6.6. The shapes of atomic orbitals
 6.7. One more electron property: Electron spin
 6.1. Electromagnetic Radiation
 Electromagnetic radiation is the radiant energy released by
electromagnetic processes.
 Atoms gain energy and they become excited. Added energy is
absorbed by electrons and then released in the form of
“Electromagnetic Radiation”
 Visible light is an example
 James Clerek Maxwell developed a mathematical theory that describes
light and other forms of radiation in terms of “wave like”, electric and
magnetic fields
 6.1. Electromagnetic Radiation
Characteristics of electromagnetic radiation
 Wavelength (λ) – symbolised by Greek letter lambda,
distance between two successive peaks or troughs in a
wave.
 Frequency (ν) – symbolised by Greek letter nu, number of
waves (cycles) that pass a point in a given unit of time,
usually per second
 Wavelength and Frequency are related to the speed at
which the wave is propagated
 Speed (c) – speed of visible light and all forms of radiation
is a constant
i.e. speed of light = 2.9979×108 m/s

𝑐𝑐 𝑚𝑚⁄𝑠𝑠 = λ 𝑚𝑚 × ν (1⁄𝑠𝑠)

𝑐𝑐 = λ × ν
 6.1. Electromagnetic Radiation
Characteristics of electromagnetic radiation

𝑐𝑐 = λ × ν
Example:

Problem: The frequency of radiation in cell phones covers a range from about
800MHz to 2 GHz, where 1 MHz = 1000 000 1/s and GHz = 1 000 000 000 1/s. What
is the wavelength (in meters) of a cell phone signal operating at 1.12 GHz?

What do you know: You are given a frequency in GHz, and a factor to convert GHz
to Hz (1/s). To calculate the wavelength of this radiation using the given equation, you
will need the speed of light, c = 2.998 X 108 m/s.

Strategy: Rearrange the equation to solve for λ. Substitute the values for the speed of
light and the frequency (first convert ν to the units 1/s) into the equation and solve.
 6.1. Electromagnetic Radiation
Characteristics of electromagnetic radiation

𝑐𝑐 = λ × ν
Solution:

GHz = 1 000 000 000 1/s = 1 X 109 Hz

Therefore 1.12 GHz = 1.12 X 109 Hz = 1.12 X 109 1/s

𝑐𝑐 = λ × ν
𝑐𝑐 2.998 × 108 𝑚𝑚⁄𝑠𝑠
λ= = 9
= 0.268 𝑚𝑚
ν 1.12 × 10 1⁄𝑠𝑠
Note: Make sure you take note of the units used in solving this problem
 6.1. Electromagnetic Radiation

The nature of waves

 Electromagnetic radiation or light consist

of oscillating or vibrating electric and
magnetic disturbances
 The electric and magnetic fields are at
right angles to each other and each wave
is described mathematically by a sine
wave.
 The intensity of light is a function of the
wave’s amplitude.
 A point of zero amplitude is called a
“node”.
 6.1. Electromagnetic Radiation
 Visible light is only a tiny portion of the electromagnetic spectrum.
 Ultraviolet (UV) radiation, that causes sunburn, has shorter wavelengths than visible light.
 X-rays and γ (gamma) rays have even shorter wavelengths
 Longer wavelengths than those of visible light starts with infrared radiation (IR)
 Microwaves and radio waves are even longer still
 6.2. Quantization: Planck, Einstein, Energy and Photons

In 1900, Max Planck suggested that electromagnetic

radiation emitted like in the image, originates from the
vibrating atoms in the heated object
He proposed that each oscillator had a fundamental
frequency of oscillation and they could only oscillate at this
frequency, or multiples of it.
𝐸𝐸 = 𝑛𝑛𝑛ν
Where 𝐸𝐸 is energy of radiation, ℎ is the proportional
constant i.e. Planck’s constant = 6.6260693 X 10-34 J.s.
The units of frequency (ν) is 1/s. Therefore the unit of
energy is Joules.
 6.2. Quantization: Planck, Einstein, Energy and Photons

An object can gain or lose energy by absorbing or

emitting radiant energy in QUANTA. A quanta of
energy is the smallest unit of energy that may be
exchanged between oscillators or emitted as
radiation. It is too small to be observed in the
classical world in which we live.

𝐸𝐸 = 𝑛𝑛𝑛ν
Planck’s constant = 6.6260693 X 10-34 J.s..
6.2. Quantization: Planck, Einstein, Energy and Photons

Einstein decided that

these observations could
be explained by
combining Planck’s
equation with a new
idea, that light has
particle like properties
6.2. Quantization: Planck, Einstein, Energy and Photons

 Certain metals will release (eject) electrons when light strikes the metal
surface.
 The energy of the light must exceed a minimum or “threshold energy” for
this to occur.
 Any excess energy beyond this minimum goes into the kinetic energy of
the ejected electron. (They fly away with greater velocity).
 Electromagnetic radiation (and all matter) exhibits wave properties and
particulate properties.
 Einstein characterised these massless particles, now called photons, as
packets of energy i.e. quanta.
 6.3. Atomic line spectra and Niels Bohr

 When a high voltage is applied to atoms of an

element in the gas phase at low pressure, the
atoms absorb the energy and are said to be
excited. The excited atoms can then emit light.
 Familiar example is neon signs
 The light from excited atoms consist of only a
few wavelengths of light therefore only a
certain colour is seen.
6.3. Atomic line spectra and Niels Bohr

 We can demonstrate this by

passing a beam of light from
excited hydrogen atoms through
a prism, only a few colours are
seen.
 This spectrum is obtained in this
manner is called a line emission
spectrum.
 Only certain energies are allowed
for the electron in the hydrogen
atom.
 Energy of the electron in the
hydrogen atom is quantized.
 6.3. Atomic line spectra and Niels Bohr

 Each element has a unique emission spectrum as shown below, for

hydrogen, mercury and neon.
 These characteristic lines in the emission spectrum can be used in
chemical analysis, to identify the element as well as determine how much
of it is in a mixture.
6.3. Atomic line spectra and Niels Bohr

 Early view of the atomic structure: Electron in a hydrogen

atom moves around the nucleus only in certain allowed
circular orbits.
1. Any orbit should be possible and so is any energy.
2. But a charged particle moving in an electric field should
emit energy.
End result should be destruction!
6.3. Atomic line spectra and Niels Bohr

 Bohr asserted that line spectra of

elements indicated that the electrons
were confined to specific energy states
called orbits.
 Bohr postulated that certain orbits
correspond to particular energy levels.
 As long as an electron is in one of the
energy levels, the system would be
+ stable
 Bohr introduced quantization into the
description of the electronic structure.
 Bohr’s model gave hydrogen atom
energy levels consistent with the
hydrogen emission spectrum.
 6.3. Atomic line spectra and Niels Bohr

 Ground state – lowest possible

energy state (n = 1)

 Electronic Transitions in the Bohr

Model for the Hydrogen Atom

An Orbit-Transition Diagram, which

accounts for the experimental
spectrum
 6.3. Atomic line spectra and Niels Bohr

 Ground state – lowest possible

energy state (n = 1)

 Electronic Transitions in the Bohr

Model for the Hydrogen Atom

An Energy-Level Diagram for

Electronic Transitions
 6.3. Atomic line spectra and Niels Bohr

 For a single electron transition from

one energy level to another:
 ΔE = change in energy of the atom
(energy of the emitted photon)
 6.3. Atomic line spectra and Niels Bohr

𝑹𝑹𝑹𝑹𝑹𝑹
 For a single electron transition from one 𝑬𝑬𝒏𝒏 = − 𝟐𝟐
energy level to another: 𝒏𝒏
 ΔE = change in energy of the atom
(energy of the emitted photon)
∆𝐸𝐸 = 𝐸𝐸𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 − 𝐸𝐸𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
n =5

energy 𝑅𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅𝑅

∆𝐸𝐸 = − − −
in 𝑛𝑛2𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑛𝑛2 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
n =2
 6.3. Atomic line spectra and Niels Bohr
𝑅𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅𝑅
∆𝐸𝐸 = − − −
𝑛𝑛2𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑛𝑛2 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• nfinal = integer; final distance from
the nucleus 1 1
∆𝐸𝐸 = −𝑅𝑅𝑅𝑅𝑅 −
𝑛𝑛2𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑛𝑛2 𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
• ninitial = integer; initial distance
from the nucleus

𝑅𝑅𝑅𝑅𝑅 = (1,097 × 107 𝑚𝑚−1 )(6,626 × 10−34 𝐽𝐽. 𝑠𝑠)(2,998 × 108 𝑚𝑚/𝑠𝑠)

𝑅𝑅𝑅𝑅𝑅 = −2,179 × 10−18 𝐽𝐽

−𝟏𝟏𝟏𝟏
𝟏𝟏 𝟏𝟏
∆𝑬𝑬 = −𝟐𝟐, 𝟏𝟏𝟏𝟏𝟏𝟏 × 𝟏𝟏𝟏𝟏 𝑱𝑱 −
𝒏𝒏𝟐𝟐 𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇 𝒏𝒏𝟐𝟐 𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊𝒊
 6.3. Atomic line spectra and Niels Bohr

 Bohr’s model, introducing quantization into a description of the atom, tied the
unseen (the structure of the atom) to the seen (the observable lines in the
hydrogen spectrum).
 This is important because agreement between theory and experiment is taken
as evidence that the theoretical model is valid.
 Nonetheless, the theory was imperfect. This model of the atom explained only
the spectrum of hydrogen atoms and of other systems having one electron
(such as ), but it failed for all other systems.
 A better model of electronic structure was needed.
6.4. Particle-wave duality: Prelude to quantum mechanics

 Recap: The photoelectric effect showed that light had wave-like and
particle-like properties i.e. a wave-particle duality
 Can particles of matter, such as electrons be viewed in the same way?
 Louie De Broglie proposed that a free electron of mass 𝑚𝑚 moving with a
velocity ν should be associated with a wavelength λ
𝒉𝒉
𝝀𝝀 =
𝒎𝒎𝝂𝝂

 Where ℎ is Plancks constant = 6,626 × 10−34 𝐽𝐽. 𝑠𝑠 or 6,626 × 10−34 𝑘𝑘𝑘𝑘. 𝑚𝑚2 /𝑠𝑠 2
6.4. Particle-wave duality: Prelude to quantum mechanics

𝒉𝒉
𝝀𝝀 =
𝒎𝒎𝝂𝝂
Q: Calculate the wavelength associated with an electron of mass 9,109 X 10-28g that
travels at 40% of the speed of light.
6.4. Particle-wave duality: Prelude to quantum mechanics

 De Broglie called the wave corresponding to the

wavelength from this equation a “matter wave”
 Matter has wave properties which are observable
for small pieces of matter like electrons
 A beam of electrons was passed through a thin
film of magnesium oxide.
 In 1927, C. J. Davisson (1881–1958) and L. H.
Germer (1896–1971) found that diffraction, a
property of waves, was observed when a beam of
electrons was directed at a thin sheet of metal
foil.
 6.5. The modern view of electronic structure: Wave or quantum
mechanics

 How does the wave-particle duality affect

our model of the arrangement of electrons
in atoms?
 Erwin Schrodinger developed a theory of
the behaviour of electrons in atoms called
quantum mechanics or wave
mechanics
 Schrodingers model is very complicated!
 Simplified view - standings waves
 Only certain matter waves are possible for
an electron in an atom
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 Wavefunctions: equations developed to describe these matter waves,

denoted by ψ
 Only certain wave functions are acceptable, energy of the electron in an
atom is quantized
 Solution to Schrodingers equation in a three dimensional space depend
on three integers: n, l and ml, quantum numbers
 Physical Meaning of a Wave Function owed to Max Borns intepretation
 The square of the function i.e. ψ2 indicates the probability of finding an
electron near a particular point in space.
 Probability distribution – intensity of colour is used to indicate the
probability value near a given point in space. Radius of the sphere that
encloses 90% of the total electron probability
 6.5. The modern view of electronic structure: Wave or quantum
mechanics
Radial Probability Distribution
Probability Distribution for the 1s Wave Function
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 Bohrs model of the atom accurately described the energy and location
of the electron
 Werner Heisenberg postulated that for a tiny object such as the
electron, it is impossible to determine accurately both its position and
location

If we choose to know the energy of an electron in an atom with only a

small uncertainty, then we must accept a correspondingly large
uncertainty in its position
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 Wavefunctions for an electron in an atom describes the

atomic orbital
 When an electron has a particular wavefunction it is said to
“occupy” a particular orbital with a given energy
 Each orbital is described by quantum numbers: n, l and ml
 n = principle quantum number, determines the energy and
size of orbital. Same n value = same electron shell. Value 1
to ∞
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 l = orbital angular momentum quantum

number. Orbitals of an electron shell can be
grouped into different subshells with a
different value of l. Value of 0 to n-1.
Determines the orbital shape. Subshells
are defined by letters.

 ml = magnetic quantum number is related to

the orientation in space of the orbitals within
a subshell. Value from –l to +l
6.5. The modern view of electronic structure: Wave or quantum
mechanics
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 For l = 2, determine the magnetic quantum numbers

(ml) and the number of orbitals.

magnetic quantum numbers = –2, – 1, 0, 1, 2

number of orbitals = 5
6.5. The modern view of electronic structure: Wave or quantum
mechanics

 For principal quantum level n = 3, determine the

number of allowed subshells (different values of l),
and give the designation of each.

# of allowed subshells = 3
l = 0, 3s
l = 1, 3p
l = 2, 3d
 6.6. The shapes of atomic orbitals

The region in which an electron can be found within an

atom

What does an orbital look like?

To answer these questions, we have to look at the

wavefunctions of the orbitals and thereby the
quantum numbers!
 6.6. The shapes of atomic orbitals

A 1s orbital is associated with the quantum

numbers n = 1 and l = 0 and ml = 0

One s-orbital that extends in a radial manner

from the nucleus forming a spherical shape
6.6. The shapes of atomic orbitals
 6.6. The shapes of atomic orbitals

 Two Representations of the

Hydrogen 1s, 2s, and 3s
Orbitals
 All s-orbitals are spherical in
shape
 The size of the orbital
increases as n increases
 6.6. The shapes of atomic orbitals

 All atomic orbital with l = 1 (p-orbitals) have the same

basic shape
 Often described as a weight lifters dumbbell
 A p-orbital has a nodal surface, a surface on which
the probability of finding the electron is zero, which
passes through the nucleus
 There are three p-orbitals in a subshell
 6.6. The shapes of atomic orbitals

 The three degenerate p-orbitals spread out on the x, y & z

axis, 90° apart in space. They are labelled according to the
axis along which they lie
 6.6. The shapes of atomic orbitals

 Note: the value of l is

equal to the number of
nodal surfaces slicing
through the nucleus
 Five d-orbitals for which l
= 2, has two nodal
surfaces
6.6. The shapes of atomic orbitals

The Boundary
Surfaces of All of the
3d Orbitals
6.6. The shapes of atomic orbitals

 s-orbitals have no nodal planes

(l = 0)
 p-orbitals have one nodal plane
(l = 1)
 d-orbitals therefore have two nodal
planes (l = 2)
6.6. The shapes of atomic orbitals
6.6. The shapes of atomic orbitals

 Representation of
the 4f Orbitals in
Terms of Their
Boundary
Surfaces
6.7. One more electron property: Electron spin

 Each orbital can accommodate no more than 2 electrons

 Since each electron is unique, we need a way to distinguish
the individual electrons in an orbital from one another.
 This is done via the 4th quantum number, “ms”.
 If atoms with a single unpaired electron are placed in a
magnetic field, they showed there are two orientations for the
atoms.
 The electron spin was aligned with the field or opposed to the
field.
6.7. One more electron property: Electron spin

Since there were 2 pathways in the Stern-Gerlach experiment,

there must be 2 spins affected by the magnetic field. One
spinning to the right, one spinning to the left.

Each “spin state” is assigned

a quantum number
ms = ± ½
+ ½ for “spin up”
− ½ for “spin down”
6.7. One more electron property: Electron spin

When it was recognised that electron spin is

quantized, scientists realised that a complete
description of an electron in any atom requires
four quantum numbers: n, l, ml and ms