Chapter 6: Electronic

Structure of Atoms
Learning Outcomes:
Calculate the wavelength of electromagnetic radiation given its frequency or its frequency given its
wavelength.
Order the common kinds of radiation in the electromagnetic spectrum according to their wavelengths
or energy.
Explain what photons are and be able to calculate their energies given either their frequency or
wavelength.
Explain how line spectra relate to the idea of quantized energy states of electrons in atoms.
Calculate the wavelength of a moving object.
Explain how the uncertainty principle limits how precisely we can specify the position and the
momentum of subatomic particles such as electrons.
Relate the quantum numbers to the number and type of orbitals and recognize the different orbital
shapes.
Interpret radial probability function graphs for the orbitals.
Explain how and why the energies of the orbitals are different in a many-electron atom from those in
the hydrogen atom.
Draw an energy-level diagram for the orbitals in a many-electron atom and describe how electrons
populate the orbitals in the ground state of an atom, using the Pauli exclusion principle and Hund’s rule.
Use the periodic table to write condensed electron configurations and determine the number of
unpaired electrons in an atom.

Waves

• To understand the electronic structure of atoms, one must

understand the nature of electromagnetic radiation.
• The distance between corresponding points on adjacent waves is
the wavelength ().
• The number of waves passing a given point per unit of time is the
frequency ().
• For waves traveling at the same velocity, the longer the
wavelength, the smaller the frequency.

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 Electromagnetic Radiation
• All electromagnetic radiation travels at the same velocity in a
vacuum: the speed of light (c), c = 3.00  108 m/s.
• The speed of a wave is the product of its wavelength () and
frequency (). c = 

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 The Nature of Energy

• The wave nature of light does not

explain how an object can glow
when its temperature increases.
• Max Planck explained it by
assuming that energy comes in
packets called quanta.
• These quanta were assumed to
be absorbed or emitted by
matter.

The Nature of Energy

• Einstein used this assumption to Photoelectric effect -

explain the photoelectric effect. the emission of
electrons from metal
• He concluded that energy is surfaces on which
proportional to frequency: light is shone

E = h
where h is Planck’s constant,
6.62610−34 J·s.
• Therefore, if one knows the
wavelength of light, one can
calculate the energy in one
photon of that light:
c =  and E = h

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 • One does not observe a
continuous spectrum, as
one gets from a white light
source.
• A line spectrum of discrete
wavelengths is observed
for elements.

• Johann Balmer discovered a simple formula

relating the four lines to integers.
• Johannes Rydberg advanced this formula.
(RH is called the Rydberg constant.)

where RH = 1.096776  107 m-1

and n2 is larger than n1
• Neils Bohr explained why this mathematical
relationship works.

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 Energy Levels in the Bohr Model
Niels Bohr adopted Planck’s assumption and
explained these phenomena:
1. Electrons in an atom can only occupy certain
orbits (corresponding to certain energies).

2. Electrons in permitted orbits have specific,

“allowed” energies; these energies will not be
radiated from the atom.
3. Energy is only absorbed or emitted in such a
way as to move an electron from one “allowed”
energy state to another; the energy is defined by:
E = h
The energy absorbed or emitted from the process
of electron promotion or demotion can be
calculated by the equation:

where ni and nf are the initial and final energy

levels of the electron.

A positive ΔE means energy is absorbed. A photon is absorbed in

this instance, when nf > ni.

A negative ΔE means energy is released. A photon is emitted in

this instance, when nf < ni.

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5
 The Wave Nature of Matter

• Louis de Broglie posited that if light can

have material properties, matter should
exhibit wave properties.
• He demonstrated that the relationship h
between mass and wavelength was  =
mv

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The Uncertainty Principle

• Heisenberg showed that the more precisely the
momentum (mv) of a particle is known, the less
precisely is its position (x) known:
h
(x) (mv) 
4

1 J = 1 kg m2 / s2

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6
 Quantum Mechanics
• Erwin Schrödinger developed a mathematical treatment into
which both the wave and particle nature of matter could be
incorporated.
• It is known as quantum mechanics.

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Quantum Mechanics
• The wave equation is designated
with a lower case Greek psi ().
• The square of the wave equation,
2, gives a probability density map
of where an electron has a certain
statistical likelihood of being at
any given instant in time.
• Solving the Schroedinger wave
equation gives a set of wave
functions, or orbitals, and their
corresponding energies.
• Each orbital describes a spatial
distribution of electron density.
• An orbital is described by a set of
three quantum numbers.
• A fourth quantum number
describes the spin of the electron.

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 Principal Quantum Number, n
• The principal quantum number, n, describes the
energy level on which the orbital resides.
• The values of n are integers ≥ 1.

Angular Momentum Quantum Number, l

• This quantum number defines the shape of the orbital.
• Allowed l values are integers ranging from 0 to n − 1.
• Letter designations to communicate the different values
of l and, therefore, the shapes and types of orbitals.

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Magnetic Quantum Number, ml

• Describes the three-dimensional orientation of the orbital. Values
are integers ranging from -l to l:
−l ≤ ml ≤ l
• Therefore, on any given energy level, there can be up to 1 s
orbital, 3 p orbitals, 5 d orbitals, 7 f orbitals, etc.
• Orbitals with the same value of n form a shell.
• Different orbital types within a shell are subshells.

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8
 Energies of Orbitals
• For a one-electron hydrogen
atom, orbitals with the same
n have the same energy.
That is, they are degenerate.
• As the number of electrons
increases, though, so does
the repulsion between them.
• Therefore, in many-electron
atoms, orbitals on the same
n are no longer degenerate.

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Radial probability functions

• Show the probability of finding the electron as a function of
the distance from the nucleus.
• As n increases, so does the most likely distance at which to
find the electron.

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 s Orbitals
• Value of l = 0.
• Spherical in shape.
• Radius of sphere increases with increasing value of n.

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s Orbitals

Observing a graph of
probabilities of finding
an electron versus
distance from the
nucleus, we see that s
orbitals possess n−1
nodes, or regions where
there is 0 probability of
finding an electron.

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 p Orbitals
• Value of l = 1.
• Have two lobes with a node between them.
• The subscript denotes axis along which the orbital
is aligned

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d Orbitals
• Value of l is 2.
• Four of the five orbitals have 4 lobes; the other
resembles a p orbital with a torus around the center.

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 General energy ordering of orbitals for a many-electron atom.

Transition metals fill the 4s by followed Each orbital box can hold
by filling 3d in the 4th period. up to two electrons.

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Spin Quantum Number, ms

• In the 1920s, it was
discovered that two electrons
in the same orbital do not
have exactly the same energy.
• The “spin” of an electron
describes its magnetic field,
which affects its energy.
• This led to a fourth quantum
number, the spin quantum
number, ms.
• The spin quantum number has
only 2 allowed values: +1/2
and −1/2.

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 Quantum Numbers
name values description

n principle 1, 2, 3... SHELL:

distance,
energy En

l angular 0, 1, 2... n-1 SUBSHELL

momentum orbital shape

ml magnetic -l,...-1, 0, orbital

+1, ...+l orientation

ms electron spin +½, -½ electron spin

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Pauli Exclusion Principle

• No two electrons in the

same atom can have
exactly the same
energy.
• No two electrons in the
same atom can have
identical set of four
quantum numbers n, l,
ml, and ms.

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 Orbital Diagrams
• Each box represents one orbital.
• Half-arrows represent the electrons.
• The direction of the arrow
represents the spin of the electron.

Hund’s Rule
For degenerate orbitals, the
lowest energy is attained when
O
the number of electrons with
the same spin is maximized.

Aufbau Principle
Electrons are added to the lowest energy
orbitals available.

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Periodic Table

• Fill orbitals in
increasing order
of energy.
• Different blocks
on the periodic
table correspond
to different
types of orbitals.

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29

Writing Atomic Electron Configurations

• The way electrons are distributed in an
atom is called its electron configuration.
• The most stable organization is the lowest
possible energy, called the ground state.
• Each component consists of
–a number denoting the energy level;
Mn, atomic number = 25, the complete electron
configuration is 1s22s22p63s23p64s23d5. The condensed
electron configuration is [Ar]4s23d5
core e- valence e-

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 Electron Configurations
and the Periodic Table

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 Anomalies
Some irregularities occur when there are
enough electrons to half-fill or completely-fill
s and d orbitals on a given row.
•Electron configuration for chromium (Cr):
[Ar] 4s13d5 rather than [Ar]4s23d4.
•Electron configuration for copper (Cu):
[Ar] 4s13d10 rather than [Ar]4s23d9.
• Others:
Mo [Kr]5s14d5
Ag [Kr]5s14d10
Au [Xe]4f146s15d10
La [Xe]6s25d1
Ce [Xe]6s24f15d1

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