CHEM 1600 Chapter 6

Chapter 6
Electronic Structure of Atoms
Electronic
Structure
of Atoms
© 2015 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
A wave is a continuously repeating
change or oscillation in matter or in a
physical field.
Light is an electromagnetic wave,

consisting of oscillations in electric and
magnetic fields traveling through space.
Electronic
Structure
7 of
| 3Atoms
Characterizing Waves
• The amplitude is the height of the wave.
– The distance from node to crest or node
to trough.
– The amplitude is a measure of light intensity—the
larger the amplitude, the brighter the light.
• The wavelength (l) is a measure of the distance

covered by the wave.
– The distance from one crest to the next
• The distance from one trough to the next, or the
distance between alternate nodes
Electronic
Structure
of Atoms
Wave Characteristics
Electronic
Structure
of Atoms
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 (). Electronic
Structure
of Atoms
Waves
• 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.
• 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
Electromagnetic Radiation
• All electromagnetic radiation travels at the same

velocity: The speed of light (c) is 3.00  108 m/s.
c = 
Electronic
Structure
of Atoms
Wavelength and frequency are related by
the wave speed. The speed of light, c, is
3.00 x 108 m/s.
c = nl
The relationship between wavelength and

frequency due to the constant velocity of
light is illustrated on the next slide. Electronic
Structure
7 of
| 9Atoms
When the
wavelength
is reduced
by a factor of
two, the
frequency
increases by
a factor of
two.
Electronic
Structure
7 | of
10Atoms
What is the wavelength of blue light
with a frequency of 6.4  1014/s?
n = 6.4  1014/s c = nl so
c = 3.00  108 m/s l = c/n
8 m
3.00 x 10
c s
λ 
 14 1
6.4 x 10
s
l = 4.7  10−7 m
Electronic
Structure
7 | of
11Atoms
The range of frequencies and
wavelengths of electromagnetic radiation
is called the electromagnetic spectrum.
Electronic
Structure
7 | of
12Atoms
Concept Check 7.1
Laser light of a specific frequency falls on a crystal that
converts a portion of this light into light with double the
original frequency. How is the wavelength of this
frequency- doubled light related to the wavelength of the
original laser light? Suppose the original laser light was
red. In which region of the spectrum would the frequency-
doubled light be? (If this is in the visible region, what
color is the light?)
When frequency is doubled, wavelength is
halved.
The light would be in the blue-violet region.
Electronic
Structure
7 | of
13Atoms
Interference
• The interaction between waves is called
interference.
• Constructive interference: When waves

interact so that they add to make a larger
wave, it is called in phase.
• Destructive interference: When waves

interact so that they cancel each other, it is
called out
of phase. Electronic
Structure
of Atoms
Interference
Electronic
Structure
of Atoms
One property of waves is that they can be
diffracted—that is, they spread out when
they encounter an obstacle about the size
of the wavelength.
In 1801, Thomas Young, a British

physicist, showed that light could be
diffracted. By the early 1900s, the wave
theory of light was well established.
Electronic
Structure
7 | of
16Atoms
Diffraction
• When traveling waves encounter an obstacle
or opening in a barrier that is about the same
size as the wavelength, they bend around it;
this is called diffraction.
– Traveling particles do not diffract.
• The diffraction of light through two slits
separated by a distance comparable to the
wavelength results in an interference
pattern of the diffracted waves.
• An interference pattern is a characteristic of
all light waves. Electronic
Structure
of Atoms
Diffraction
Electronic
Structure
of Atoms
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
The Nature of Energy—Quanta
Max Planck
explained it by
assuming that
energy comes
in packets
called quanta
(singular:
quantum).
Electronic
Structure
of Atoms
The wave theory could not explain the
photoelectric effect, however.
Electronic
Structure
7 | of
21Atoms
The
photoelectric
effect is the
ejection of an
electron from
the surface of a
metal or other
material when
light shines on
it.
Electronic
Structure
7 | of
22Atoms
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 = h
where h is Planck’s constant,
6.626  10−34 J∙s.
Electronic
Structure
of Atoms
Einstein used this understanding of light
to explain the photoelectric effect in 1905.
Each electron is struck by a single

photon. Only when that photon has
enough energy will the electron be
ejected from the atom; that photon is said
to be absorbed.
Electronic
Structure
7 | of
24Atoms
Complementary Properties
• When you try to observe the wave nature of the
electron, you cannot observe its particle nature, and
vice versa.
– Wave nature = interference pattern
– Particle nature = position, which slit it is passing
through
• The wave and particle nature of the electron are
complementary properties.
– As you know more about one you know less about
the other.
Electronic
Structure
of Atoms
Light, therefore, has properties of both
waves and matter. Neither understanding
is sufficient alone. This is called the
particle–wave duality of light.
Electronic
Structure
7 | of
26Atoms
The blue–green line of the hydrogen atom
spectrum has a wavelength of 486 nm.
What is the energy of a photon of this
light?
E = hn and
l = 486 nm = 4.86  10−7 m c = nl so
c = 3.00  108 m/s E = hc/l
h = 6.63  10−34 J  s
 8 m
hc

6.63  10 Js  3.00  10

34
s 


E 
λ 4.86  107 m  
Electronic
E = 4.09  10 −19
J Structure
7 | of
27Atoms
In the early 1900s, the atom was
understood to consist of a positive
nucleus around which electrons move
(Rutherford’s model).
This explanation left a theoretical

dilemma: According to the physics of the
time, an electrically charged particle
circling a center would continually lose
energy as electromagnetic radiation. But
this is not the case—atoms are stable.
Electronic
Structure
7 | of
28Atoms
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
A continuous spectrum contains all
wavelengths of light.
A line spectrum shows only certain

colors or specific wavelengths of light.
When atoms are heated, they emit light.
This process produces a line spectrum
that is specific to that atom. The emission
spectra of six elements are shown on the
next slide.
Electronic
Structure
7 | of
30Atoms
Electronic
Structure
7 | of
31Atoms
Copyright © Cengage Learning. All rights reserved.
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
The Hydrogen Spectrum
• Johann Balmer (1885) discovered a

simple formula relating the four lines to
integers.
• Johannes Rydberg advanced this
formula.
• Neils Bohr explained why this

mathematical relationship works. Electronic
Structure
of Atoms
Transitions Between Energy Levels
An electron can change energy levels by
absorbing energy to move to a higher
energy level or by emitting energy to move
to a lower energy level.
Electronic
Structure
7 | of
34Atoms
Light is absorbed by an atom when the
electron transition is from lower n to
higher n (nf > ni). In this case, DE will be
positive.
Light is emitted from an atom when the

electron transition is from higher n to
lower n (nf < ni). In this case, DE will be
negative.
An electron is ejected when nf = ∞.
Electronic
Structure
7 | of
35Atoms
The Bohr Model
• Niels Bohr adopted Planck’s
assumption and explained
these phenomena in this way:
1. Electrons in an atom can
only occupy certain orbits
(corresponding to certain
energies).
Electronic
Structure
of Atoms
The Bohr Model
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
Electronic
Structure
of Atoms
The Bohr Model
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation
1 1
E = −hcRH ( nf2
–
ni2 )
where RH is the Rydberg
constant, 1.097  107 m−1, and ni
and nf are the initial and final
energy levels of the electron.Electronic
Structure
of Atoms
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
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.
2) Energy is involved in the transition of
an electron from one level to another.
Electronic
Structure
of Atoms
Concept Check 7.2
An atom has a line spectrum consisting of a red
line and a blue line. Assume that each line
corresponds to a transition between two adjacent
energy levels. Sketch an energy-level diagram
with three energy levels that might explain this
line spectrum, indicating the transitions on this
diagram. Consider the transition from the highest
energy level on this diagram to the lowest energy
level. How would you describe the color or region
of the spectrum corresponding to this transition?
Electronic
Structure
7 | of
41Atoms
Copyright © Cengage Learning. All rights reserved.
A minimum of three energy levels are required.
n=3
n=2
n=1
The red line corresponds to the smaller energy
difference in going from n = 3 to n = 2.
The blue line corresponds to the larger energy
difference in going from n = 2 to n = 1.
Electronic
Structure
7 | of
42Atoms
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
h
The wave nature of light  = mv
is used to produce this
electron micrograph. Electronic
Structure
of Atoms
In 1923, Louis de Broglie, a French
physicist, reasoned that particles (matter)
might also have wave properties.
The wavelength of a particle of mass, m

(kg), and velocity, v (m/s), is given by the
de Broglie relation:
h
λ
mv
h  6.626  1034 J  s
Electronic
Structure
7 | of
44Atoms
Compare the wavelengths of
(a) an electron traveling at a speed that is
one-hundredth the speed of light and (b) a
baseball of mass 0.145 kg having a speed
of 26.8 m/s (60 mph).
Electron Baseball
me = 9.11  10−31 kg m = 0.145 kg h
λ
v = 3.00  106 m/s v = 26.8 m/s mv
Electronic
Structure
7 | of
45Atoms
Electron
me = 9.11  10−31 kg
v = 3.00  106 m/s
6.63  1034 J  s
λ  2.43  10−10 m
 6 m
 31
9.11  10 kg  3.00  10
 s



Baseball
m = 0.145 kg
v = 26.8 m/s
34
6.63  10 J  s
λ  1.71  10−34 m
 m
 0.145 kg  26.8 
 s  Electronic
Structure
7 | of
46Atoms
The Uncertainty Principle
Heisenberg showed
that the more precisely
the momentum of a
particle is known, the
less precisely is its
position is known:
h
(x) (mv) 
4
Electronic
Structure
of Atoms
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
Quantum mechanics alters how we think
about the motion of particles.
In 1927, Werner Heisenberg showed how it
is impossible to know with absolute precision
both the position, x, and the momentum, p,
of a particle such as electron.
h
(Δx )(Δp ) 
4π
Because p = mv this uncertainty becomes

more significant as the mass of the particle
becomes smaller.
Electronic
Structure
7 | of
49Atoms
Quantum mechanics allows us to make
statistical statements about the regions in
which we are most likely to find the electron.
Solving Schrödinger’s equation gives us a

wave function, represented by the Greek
letter psi, y, which gives information about a
particle in a given energy level.
Psi-squared, y 2, gives us the probability of

finding the particle within a region of space.
Electronic
Structure
7 | of
50Atoms
Quantum Mechanics
• The solution of Schrödinger’s
wave equation is designated with
a lowercase Greek psi ().
• The square of the wave equation,
2, gives the electron density, or
probability of where an electron is
likely to be at any given time.
Electronic
Structure
of Atoms
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
According to quantum mechanics, each
electron is described by four quantum numbers:
1. Principal quantum number (n)

2. Angular momentum quantum number (l)
3. Magnetic quantum number (ml)
4. Spin quantum number (ms)
The first three define the wave function for a

particular electron. The fourth quantum number
refers to the magnetic property of electrons.
Electronic
Structure
7 | of
53Atoms
A wave function for an electron in an atom
is called an atomic orbital (described by
three quantum numbers—n, l, ml).
It describes a region of space with a

definite shape where there is a high
probability of finding the electron.
We will study the quantum numbers first,

and then look at atomic orbitals.
Electronic
Structure
7 | of
54Atoms
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
Principal Quantum Number, n
This quantum number is the one on which
the energy of an electron in an atom
primarily depends. The smaller the value
of n, the lower the energy and the smaller
the orbital.
The principal quantum number can have
any positive value: 1, 2, 3, . . .
Orbitals with the same value for n are said
to be in the same shell.
Electronic
Structure
7 | of
56Atoms
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.
• We use letter designations to communicate
the different values of l and, therefore, the
shapes and types of orbitals.
Electronic
Structure
of Atoms
Angular Momentum Quantum Number,
l
This quantum number distinguishes
orbitals of a given n (shell) having
different shapes.
It can have values from 0, 1, 2, 3, . . . to a
maximum of (n – 1).
For a given n, there will be n different
values of l, or n types of subshells.
Orbitals with the same values for n and l
are said to be in the same shell and
subshell. Electronic
Structure
7 | of
58Atoms
Subshells are sometimes designated by
lowercase letters:
l 0 1 2 3 ...
Letter s p d f
n≥ 1 2 3 4
Not every subshell type exists in every shell.

The minimum value of n for each type of
subshell is shown above.
Electronic
Structure
7 | of
59Atoms
Angular Momentum Quantum
Number (l)
Electronic
Structure
of Atoms
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:
−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
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
Atomic Orbital Shapes
An s orbital is spherical.
A p orbital has two lobes along a straight

line through the nucleus, with one lobe on
either side.
A d orbital has a more complicated shape.
Electronic
Structure
7 | of
63Atoms
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
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
p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.
Electronic
Structure
of Atoms
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
f Orbitals
• Very complicated shapes (not shown

in text)
• Seven equivalent orbitals in a sublevel
• l=3
Electronic
Structure
of Atoms
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
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
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
Pauli Exclusion Principle
• No two electrons in the same atom can
have exactly the same energy.
• Therefore, no two electrons in the same
atom can have identical sets of quantum
numbers.
• 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
Which of the following are permissible
sets of quantum numbers?
n = 4, l = 4, ml = 0, ms = ½
n = 3, l = 2, ml = 1, ms = -½
n = 2, l = 0, ml = 0, ms = ³/²
(a) Notn permitted.

= 5, l = 3,When
ml = -3,
n =m = ½maximum
4,s the
value of l is 3.
(b) Permitted.
(c) Not permitted; ms can only be +½ or –½.
(b) Permitted. Electronic
Structure
7 | of
73Atoms
Electron Configurations
• The way electrons are distributed in an
4p 5 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;
Electronic
Structure
of Atoms
– a letter denoting the type of orbital;
Electronic
Structure
of Atoms
– a letter denoting the type of orbital;
– a superscript denoting the number of
electrons in those orbitals.
Electronic
Structure
of Atoms
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
Hund’s Rule
“For degenerate
orbitals, the
lowest energy is
attained when
the number of
electrons with
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 same spin,
Electronic
as much as possible. Structure
of Atoms
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
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)
Electronic
Structure
of Atoms
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
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

CHEM 1600 Chapter 6

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CHEM 1600 Chapter 6

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Chapter 6

Electronic Structure of Atoms

Light is an electromagnetic wave,

• The wavelength (l) is a measure of the distance

• To understand the electronic structure of

• All electromagnetic radiation travels at the same

The relationship between wavelength and

• Constructive interference: When waves

• Destructive interference: When waves

In 1801, Thomas Young, a British

The wave nature of light

Each electron is struck by a single

This explanation left a theoretical

A line spectrum shows only certain

• Johann Balmer (1885) discovered a

• Neils Bohr explained why this

Light is emitted from an atom when the

• It only works for hydrogen!

The wavelength of a particle of mass, m

Because p = mv this uncertainty becomes

Solving Schrödinger’s equation gives us a

Psi-squared, y 2, gives us the probability of

• Solving the wave equation gives a set

1. Principal quantum number (n)

The first three define the wave function for a

It describes a region of space with a

We will study the quantum numbers first,

• The principal quantum number, n,

Not every subshell type exists in every shell.

• The magnetic quantum number describes the

A p orbital has two lobes along a straight

A d orbital has a more complicated shape.

• The value of l for s orbitals is 0.

• Very complicated shapes (not shown

(a) Notn permitted.

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

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