Chemistry: The Central Science

Fourteenth Edition

Chapter 6
Electronic Structure of Atoms

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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!

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Waves (1 of 2)

• 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 .
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Waves (2 of 2)
• 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.

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Electromagnetic Radiation (1 of 2)

• All electromagnetic radiation travels at the same

velocity: The speed of light (c) is 3.00 × 108 m/s.
c  λv
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Electromagnetic Radiation (2 of 2)
Table 6.1 Common Wavelength Units for Electromagnetic Radiation
Unit Symbol Length (m) Type of Radiation
10 to the negative
Angstrom ​Å 10 10
tenth X ray
10 to the negative
Nanometer nm ninth
10 9 Ultraviolet, visible
Mu m 10 to the negative
Micrometer μm sixth 6
10 Infrared
10 to the negative
Millimeter mm third 3
10 Microwave
10 to the negative
Centimeter cm second
2 Microwave
10
Meter m 1 Television, radio
Kilometer km 1000 Radio

• 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.
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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)

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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.

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The Nature of Energy—Quanta
Max Planck explained it by
assuming that energy comes
in packets called quanta
(singular: quantum).

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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.

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Atomic Emissions
Another mystery in the early twentieth century involved
the emission spectra observed from energy emitted by
atoms and molecules.

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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.

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The Hydrogen Spectrum

• Johann Balmer (1885) discovered a simple formula

relating the four lines to integers.
• Johannes Rydberg advanced this formula. (R H is
called the Rydberg constant.)
1  1 1 
RH  2  2 
λ  n1 n2 
• Neils Bohr explained why this mathematical
relationship works.
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The Bohr Model (1 of 3)
• 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.

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The Bohr Model (2 of 3)
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 emitter of absorbed
as a photon that has energy
E = h.
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The Bohr Model (3 of 3)
• Electrons in the lowest energy
state are in the ground state.
• Any energy higher is called an
excited state.
• Since each orbit as a specific
value compared to RH,
transitions from one energy
level to another can be
calculated:
 1 1 
E Ef  Ei  2.18 10  18
J  2  2 
 nf ni 
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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.

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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.

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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.

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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
λ is used to produce this
mv electron micrograph.

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

h
x mv  
4π

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Quantum Mechanics (1 of 2)
• 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.

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Quantum Mechanics (2 of 2)
• 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.

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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.

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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.
• These correspond to the values in the Bohr model.

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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.

Value of l 0 1 2 3

Letter used s p d f

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Magnetic Quantum Number (ml) (1 of 2)
• 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.

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Magnetic Quantum Number (ml) (2 of 2)
• Orbitals with the same value of n form an electron shell.
• Different orbital types within a shell are subshells.
Table 6.2 Relationship among Values of n, l, and ml through n = 4a
Possible Subshell Possible Number of Orbitals Total Number of
n
Values of l Designation Values of ml in Subshell Orbitals in Shell
1 0 1s 0 1 1
2 0 2s 0 1 Blank
Blan
k 1 2p 1, 0, −1 3 4
3 0 3s 0 1 Blank
Blan
k 1 3p 1, 0, −1 3 Blank
Blan
k 2 3d 2, 1, 0, −1, −2 5 9
4 0 4s 0 1 Blank
Blan
k 1 4p 1, 0, −1 3 Blank
Blan
k 2 4d 2, 1, 0, −1, −2 5 Blank
Blan
k 3 4f 3, 2, 1, 0, −1, −2, −3 7 16

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s Orbitals (1 of 2)

• 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.

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s Orbitals (2 of 2)
• 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.

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p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.

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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.

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f Orbitals
• Very complicated shapes (not shown in text)
• Seven equivalent orbitals in a sublevel
• l=3

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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.

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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.)
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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 the spin quantum
number, ms.

• The spin quantum number has only

1 1
two allowed values,  2 and  2
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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.

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Electron Configurations (1 of 3)
• 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;
5
4p

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Electron Configurations (2 of 3)
• 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

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Electron Configurations (3 of 3)
• 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.
4p5
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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.

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Hund’s Rule
“When filling degenerate Table 6.3 Electron Configurations of
Several Lighter Elements
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 same spin, as much as
possible.
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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.

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Transition Metals
• Argon (atomic number 18)
ends period 3. Its electron
configuration is
1s 2 2s 2 2 p 6 3s 2 3 p 6 .
• 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.
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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.

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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.

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Periodic Table and Electron
Configuration
• The periodic table is followed directly when
determining the electron configuration for Most
elements.

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

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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.

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