Lecture Presentation

Chapter 6

Electronic
Structure of Atoms

James F. Kirby
Quinnipiac University
Hamden, CT
© 2018 Pearson Education, Inc.
 Electronic Structure

• This chapter is all about electronic

structure—the arrangement and energy of
electrons.
• It may seem odd to start by talking about
waves. However, extremely small particles
have properties that can only be explained
in this manner!

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Waves

• To understand the electronic structure of atoms, one must

understand the nature of electromagnetic radiation.
• Electromagnetic radiation moves as waves through
space at the speed of light.
• The distance between corresponding points on adjacent
waves is the wavelength (λ). Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Waves
• The number of waves
passing a given point per unit
of time is the frequency (ν).
• For waves traveling at the
same velocity, the longer the
wavelength, the smaller the
frequency.
• If the time associated with
the lines to the left is one
second, then the frequencies
would be 2 s–1 and 4 s–1,
respectively. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Electromagnetic Radiation

• All electromagnetic radiation travels at the same

velocity: The speed of light (c) is 3.00 × 108 m/s.
c = λν Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Electromagnetic Radiation

• There are many types of electromagnetic radiation.

• They have different wavelengths and energies from
each other.
• The typical wavelength unit used vary based on
the lengths.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Electronic Properties NOT
Explained by Waves
• Three observed properties associated with
how atoms interact with electromagnetic
radiation can NOT be explained by waves:
1) the emission of light from hot objects (blackbody
radiation)
2) the emission of electrons from metal surfaces on
which light is shone (the photoelectric effect)
3) emission of light from electronically excited gas
atoms (emission spectra)

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Nature of Energy

The wave nature of light

does not explain how
an object can glow
when its temperature
increases.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Nature of Energy—Quanta

Max Planck explained

it by assuming that
energy comes in
packets called quanta
(singular: quantum).

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Photoelectric Effect
• Einstein used quanta to explain
the photoelectric effect.
• Each metal has a different
energy at which it ejects
electrons. At lower energy,
electrons are not emitted.
• He concluded that energy is
proportional to frequency:
E = hν
where h is Planck’s constant,
6.626 × 10−34 J∙s. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Atomic Emissions
Another mystery in the early twentieth century
involved the emission spectra observed from
energy emitted by atoms and molecules.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Continuous vs. Line Spectra

• For atoms and molecules,

one does not observe a
continuous spectrum
(the “rainbow”), as one
gets from a white light
source.
• Only a line spectrum of
discrete wavelengths is
observed. Each element
has a unique line
spectrum.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Hydrogen Spectrum

• Johann Balmer (1885) discovered a simple

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

• Neils Bohr explained why this mathematical

relationship works. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Bohr Model
• Niels Bohr adopted
Planck’s assumption
and explained these
phenomena in this way:
1) Only orbits of certain
radii, corresponding to
specific energies, are
permitted for the
electron in a hydrogen
atom.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Bohr Model
2) An electron in a permitted
orbit is in an “allowed” energy
state. An electron in an
allowed energy state does
not radiate energy, and,
therefore, does not spiral into
the nucleus.
3) Energy is emitted or
absorbed by the electron only
as the electron changes from
one energy state to another.
This energy is is emitter of
absorbed as a photon that
has energy E = h. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Bohr Model
• Electrons in the lowest
energy state are in the
ground state.
• Any energy higher is called
an excited state.
• Since each orbit has a
specific value compared to
RH, transitions from one
energy level to another can
be calculated:
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Values of Transitions

• What do the values mean

using the Bohr Model?
• A positive ΔE means energy
is absorbed. A photon is
absorbed in this instance.
This happens if nf > ni.
• A negative ΔE means energy
is released. A photon is
emitted in this instance. This
happens if nf < ni.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Limitations of the Bohr Model

• It only works for hydrogen!

• Classical physics would result in an electron
falling into the positively charged nucleus.
Bohr simply assumed it would not!
• Circular motion is not wave-like in nature.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Important Ideas from the
Bohr Model
• Points that are incorporated into the current
atomic model include the following:
1) Electrons exist only in certain discrete energy
levels, which are described by quantum
numbers.
2) Energy is involved in the transition of an
electron from one level to another.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Wave Nature of Matter
• Louis de Broglie theorized
that if light can have
material properties, matter
should exhibit wave
properties.
• He demonstrated that the
relationship between mass
and wavelength was:
The wave nature of light h
is used to produce this λ = mv
electron micrograph. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 The Uncertainty Principle

Heisenberg showed
that the more precisely
the momentum of a
particle is known, the
less precisely its
position is known:

h
(Δx) (Δmv) 
4π
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Quantum Mechanics
• Erwin Schrödinger
developed a mathematical
treatment into which both
the wave and particle
nature of matter could be
incorporated.
• This is known as
quantum mechanics.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Quantum Mechanics
• The solution of
Schrödinger’s wave
equation for hydrogen
yields wave functions for
the electron.
• The square of the wave
function gives the
electron density, or
probability of where an
electron is likely to be at
any given time. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Quantum Numbers

• Solving the 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.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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.
• These correspond to the values in the
Bohr model.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Angular Momentum Quantum Number (l)

• This quantum number defines the shape

of the orbital.
• Allowed values of l are integers ranging
from 0 to n − 1.
• Letter designate the different values of l.
This defines the shape of the orbitals.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Magnetic Quantum Number (ml)

• The magnetic quantum number describes

the three-dimensional orientation of the
orbital.
• Allowed values of ml are integers ranging
from −l to l including 0:
−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, and so forth. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Magnetic Quantum Number (ml)
• Orbitals with the same value of n form an
electron shell.
• Different orbital types within a shell are subshells.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 s Orbitals

• The value of l for s orbitals is 0.

• They are spherical in shape.
• The radius of the sphere increases with the
value of n.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 s Orbitals
• For an ns orbital, the
number of peaks is n.
• For an ns orbital, the
number of nodes (where
there is zero probability
of finding an electron) is
n – 1.
• As n increases, the
electron density is more
spread out and there is
a greater probability of
finding an electron
further from the nucleus.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 d Orbitals

• The value of l for a

d orbital is 2.
• Four of the five d
orbitals have four
lobes; the other
resembles a p
orbital with a
doughnut around
the center.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 f Orbitals

• Very complicated shapes (not shown

in text)
• Seven equivalent orbitals in a sublevel
• l=3

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Energies of Orbitals—Hydrogen
• For a one-electron
hydrogen atom,
orbitals on the same
energy level have
the same energy.
• Chemists call them
degenerate orbitals.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Energies of Orbitals—
Many-electron Atoms
• As the number of electrons
increases, so does the repulsion
between them.
• Therefore, in atoms with more
than one electron, not all orbitals
on the same energy level are
degenerate.
• Orbital sets in the same sublevel
are still degenerate.
• Energy levels start to overlap in
energy (e.g., 4s is lower
in energy than 3d.)
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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 the spin quantum
number, ms.
• The spin quantum number has only
two allowed values, +½ and –½.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Pauli Exclusion Principle
• No two electrons in the same atom can have the
same set of four quantum numbers.
• Therefore, no two electrons in the same atom can
have the exact same energy.
• This means that every electron in an atom must
differ by at least one of the four quantum number
values: n, l, ml, and ms.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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;

4p 5 Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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;
– a letter denoting the type of orbital;

4p 5 Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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;
– a letter denoting the type of orbital;
– a superscript denoting the number of electrons in those
orbitals.

4p 5 Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Orbital Diagrams

• Each box in the

diagram represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
arrow represents the
relative spin of the
electron.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Hund’s Rule
“When filling
degenerate orbitals
the lowest energy is
attained when the
number of electrons
having the same
spin is maximized.”

• This means that, for a set of orbitals in the same

sublevel, there must be one electron in each
orbital before pairing and the electrons have the
Electronic
same spin, as much as possible. Structure
of Atoms
© 2018 Pearson Education, Inc.
 Condensed Electron Configurations
• Elements in the same group of the
periodic table have the same number
of electrons in the outer most shell.
These are the valence electrons.
• The filled inner shell electrons are
called core electrons. These include
completely filled d or f sublevels.
• We write a shortened version of an
electron configuration using brackets
around a noble gas symbol and listing
only valence electrons. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Transition Metals

• Argon (atomic number 18)

ends period 3. Its electron
configuration is
1s22s22p63s23p6.
• Potassium (atomic number 19)
might be expected to have
electrons in 3d. BUT 4s
fills next.
• Transition metals follow the
filling of 4s by filling 3d in the
4th period.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Lanthanides and Actinides
• The elements which fill the f orbitals have special
names as a portion of a period, not as a group.
• The lanthanide elements (atomic numbers
57 to 70) have electrons entering the 4f sublevel.
• The actinide elements (including Uranium, at.
no. 92, and Plutonium, at. no. 94) have electrons
entering the 5f sublevel.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Periodic Table
• We fill orbitals in increasing order of energy.
• Different blocks on the periodic table correspond to
different types of orbitals: s = blue, p = pink (s and p are
representative elements); d = orange (transition elements);
f = tan (lanthanides and actinides, or inner transition
elements)
• The s and p blocks are called the main-group elements.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Periodic Table and
Electron Configuration
• The periodic table is followed directly when
determining the electron configuration for MOST
elements.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Some Anomalies

• Some irregularities
occur when there
are enough
electrons to half-fill
s and d orbitals on
a given row.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Chromium as an Anomaly

• For instance, the electron configuration

for chromium is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.
• This occurs because the 4s and 3d
orbitals are very close in energy.
• These anomalies occur in f-block atoms
with f and d orbitals, as well. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.