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
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 Waves

• To understand the electronic structure of atoms, one

must understand the nature of electromagnetic
radiation.
• Electromagnetic radiation (radiant energy) moves as
waves through space at the speed of light.
• The distance between corresponding points on adjacentElectronic
waves is the wavelength (λ). Structure
of Atoms
© 2018 Pearson Education, Inc.
 Waves
• The number of waves passing
a given point per unit of time
is the frequency (n ; nu) –
unit is hertz (1 Hz = 1s-1)
• 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
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 The Wave Nature of Light

• Electromagnetic waves have characteristic

wavelengths and frequencies.
• The electromagnetic spectrum is a display of
the various types of electromagnetic radiation
arranged in order of increasing wavelength.
– Example: visible radiation has wavelengths
between 400 nm (violet) and 750 nm (red).

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Structure
of Atoms
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 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
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 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
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Sample Exercise 6.1 Concepts of Wavelength and Frequency
Two electromagnetic waves are represented in the
margin. (a) Which wave has the higher frequency? (b) If
one wave represents visible light and the other represents
infrared radiation, which wave is which?

Solution
(a) Wave 1 has a longer wavelength
(greater distance between peaks). The
longer the wavelength, the lower the
frequency (n = c/l). Thus, Wave 1
has the lower frequency, and Wave 2
has the higher frequency.
(b) The electromagnetic spectrum
(Figure 6.4) indicates that infrared
radiation has a longer wavelength
than visible light. Thus, Wave 1 is
infrared radiation.

Electronic
Structure
of Atoms
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Sample Exercise 6.1 Concepts of Wavelength and Frequency
Continued

Practice Exercise 1
A source of electromagnetic radiation produces infrared light. Which of the following could be the wavelength of
the light?
(a) 3.0 nm (b) 4.7 cm (c) 66.8 m (d) 34.5 µm (e) 16.5 Å

Practice Exercise 2
Which type of visible light has a longer wavelelength, red or blue light?

Electronic
Structure
of Atoms
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Sample Exercise 6.2 Calculating Frequency from Wavelength
The yellow light given off by a sodium vapor lamp used for public lighting has a wavelength of 589 nm. What is the
frequency of this radiation?

Solution
Analyze We are given the wavelength, l, of the radiation and asked to calculate its frequency, n.

Plan The relationship between the wavelength and the frequency is given by Equation 6.1. We can solve for n and
use the values of l and c to obtain a numerical answer. (The speed of light, c, is 3.00 × 108 m/s to three significant
figures.)

Solve Solving Equation 6.1 for frequency gives n = c/l. When we insert the values for c and l, we note that the
units of length in these two quantities are different. We use a conversion factor to convert the wavelength from
nanometers to meters, so the units cancel:

Check The high frequency is reasonable because of the short wavelength. The units are proper because frequency
has units of “per second,” or s–1.

Electronic
Structure
of Atoms
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Sample Exercise 6.2 Calculating Frequency from Wavelength
Continued

Practice Exercise 1
Consider the following three statements: (i) For any electromagnetic radiation, the product of the wavelength and the
frequency is a constant. (ii) If a source of light has a wavelength of 3.0 Å, its frequency is 1.0 × 1018 Hz. (iii) The
speed of ultraviolet light is greater than the speed of microwave radiation. Which of these three statements is or are
true? (a) Only one statement is true. (b) Statements (i) and (ii) are true. (c) Statements (i) and (iii) are true. (d)
Statements (ii) and (iii) are true. (e) All three statements are true.

Practice Exercise 2
(a) A laser used in orthopedic spine surgery produces radiation with a wavelength of 2.10 µm. Calculate the frequency
of this radiation. (b) An FM radio station broadcasts electromagnetic radiation at a frequency of 103.4 MHz
(megahertz; 1 MHz = 106 s–1). Calculate the wavelength of this radiation. The speed of light is 2.998 × 108 m/s to four
significant figures.

Electronic
Structure
of Atoms
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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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Structure
of Atoms
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 The Nature of Energy

• The wave (analog?)

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

Electronic
Structure
of Atoms
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 The Nature of Energy—Quanta

• Max Planck explained it

by assuming that energy
comes in packets called
quanta (singular:
quantum).
• Continuous vs. quantized
= violin vs. piano

Electronic
Structure
of Atoms
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 The Photoelectric Effect (광전효과)
• Light shining on the surface of a metal
can cause electrons to be ejected from
the metal.
– The electrons will only be ejected if the
photons have sufficient energy (work
function):
– Below the threshold (역치) frequency
no electrons are ejected.
– Above the threshold frequency, the
excess energy appears as the kinetic
energy of the ejected electrons.
– Each metal has a different energy at
which it ejects electrons. Electronic
Structure
of Atoms
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 The Photoelectric Effect

• The photoelectric effect provides evidence for

the particle nature of light.
– It also provides evidence for quantization.
– Light has wave-like AND particle-like properties.
• Einstein assumed that light travels in energy
packets called photons (광자).
– The energy of one photon is E = hn ; h is Planck’s
constant, 6.626 ´ 10−34 J-s.
– Energy is proportional to frequency

Electronic
Structure
of Atoms
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Sample Exercise 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light that has a wavelength of 589 nm.

Solution
Analyze Our task is to calculate the energy, E, of a photon, given its wavelength, l = 589 nm.

Plan We can use Equation 6.1 to convert the wavelength to frequency: n = c/l. We can then use Equation 6.3 to
calculate energy: E = hn

Solve The frequency, n, is calculated from the given wavelength, as shown in Sample Exercise 6.2:

The value of the Planck constant, h, is given both in the text and in the table of physical constants on the inside
back cover of the text; thus we can easily calculate E:

Comment If one photon of radiant energy supplies 3.37 × 10–19 J, we calculate that one mole of these photons
will supply:

Electronic
Structure
of Atoms
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Sample Exercise 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light that has a wavelength of 589 nm.

Practice Exercise 1
Which of the following expressions correctly gives the energy of a mole of photons with wavelength l?

(a) E = (b) E = (c) E = (d) E = (e) E =

Practice Exercise 2
(a) A laser emits light that has a frequency of 4.69 × 1014 s–1. What is the energy of one photon of this radiation? (b) If
the laser emits a pulse containing 5.0 × 1017 photons of this radiation, what is the total energy of that pulse? (c) If the
laser emits 1.3 × 10–2 J of energy during a pulse, how many photons are emitted?

Electronic
Structure
of Atoms
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 Line Spectra

• Radiation composed of only one wavelength is

called monochromatic.
• When radiation from a light source, such as a
lightbulb, is separated into its different
wavelength components, a continuous spectrum
is produced.

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Structure
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 Line Spectra and Atomic Emissions
• Not all radiation is continuous.
• A gas placed in a partially evacuated tube and
subjected to a high voltage produces single
colors of light.
– The spectrum that we see contains radiation of only
specific wavelengths; this is called a line spectrum
– 전자의 구조?

Electronic
Structure
of Atoms
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 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
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 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 = hn.

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Structure
of Atoms
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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. (RH is
called the Rydberg constant.)

• Neils Bohr explained why this mathematical

relationship works.
Electronic
Structure
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 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
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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.

Electronic
Structure
of Atoms
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Sample Exercise 6.4 Electronic Transitions in the Hydrogen Atom
In the Bohr model of the hydrogen atom, electrons are confined to orbits with fixed radii, and those radii can be
calculated. The radii of the first four orbits are 0.53, 2.12, 4.76, and 8.46 Å, respectively, as depicted below.
(a) If an electron makes a transition from the ni = 4 level to a lower-energy level, nf = 3, 2, or 1, which transition
would produce a photon with the shortest wavelength?
(b) What are the energy and wavelength of such a photon, and in which region of the electromagnetic spectrum
does it lie?
(c) The image on the right shows the output of a detector that measures the intensity of light emitted from a sample
of hydrogen atoms that have been excited so that each atom begins with an electron in the n = 4 state. What is
the final state, nf, of the transition being detected?

Electronic
Structure
of Atoms
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Sample Exercise 6.4 Electronic Transitions in the Hydrogen Atom
Continued

Solution
Analyze We are asked to determine the energy and wavelength associated with various transitions involving an
electron relaxing from the n = 4 state of the hydrogen atom to one of three lower-energy states.

Plan Given the integers representing the initial and final states of the electron, we can use Equation 6.6 to calculate
the energy of the photon emitted and then use the relationships E = hn and c = nl to convert energy to wavelength.
The photon with the highest energy will have the shortest wavelength because photon energy is inversely
proportional to wavelength.

Solve
(a) The wavelength of a photon is related to its energy through the relationship E = hn = hc/l. Hence, the photon
with the smallest wavelength will have the largest energy. The energy levels of the electron orbits decrease as n
decreases.

The electron loses the most energy on transitioning from the ni = 4 state to the nf = 1 state, and the photon
emitted in that transition has the highest energy and the smallest wavelength.

(b) We first calculate the energy of the photon using Equation 6.6 with ni = 4 and nf = 1:

Electronic
Structure
of Atoms
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Sample Exercise 6.4 Electronic Transitions in the Hydrogen Atom
Continued

Next we rearrange Planck’s relationship to calculate the frequency of the emitted photon.

Finally, we use the frequency to determine the wavelength.

Light with this wavelength falls in the ultraviolet region of the electromagnetic spectrum.

(c) From the graph, we estimate the wavelength of the photon to be approximately 480 nm. Starting from the
wavelength, it is easiest to estimate nf using Equation 6.4:

Rearranging:
So nf = 2, and the photons seen by the detector are those emitted when an electron transitions from the nf = 4 to
the nf = 2 state.

Electronic
Structure
of Atoms
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Sample Exercise 6.4 Electronic Transitions in the Hydrogen Atom
Continued

Check Referring back to Figure 6.12, we confirm that the n = 4 to n = 1 transition should have the largest energy of the
three possible transitions.

Practice Exercise 1
In the top part of Figure 6.11, the four lines in the H atom spectrum are due to transitions from a level for which ni > 2
to the nf = 2 level. What is the value of ni for the red line in the spectrum? (a) 3 (b) 4 (c) 5 (d) 6 (e) 7

Practice Exercise 2
For each of the following transitions, give the sign of DE and indicate whether a photon is emitted or absorbed.
(a) n = 3 to n = 1 (b) n = 2 to n = 4
Electronic
Structure
of Atoms
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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.

Electronic
Structure
of Atoms
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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 ;
quantized.
2) Energy is involved in the transition of an electron from
one level to another.

Electronic
Structure
of Atoms
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 The Wave Behavior of Matter
• Knowing that light has a particle nature, it seems
reasonable to ask whether matter has a wave nature.
• Using Einstein’s and Planck’s equations, deBroglie
derived: λ = h/mυ
– The momentum, mν (= p), is a particle property, whereas λ is a
wave property.
– Matter waves (물질파) are the term used to describe wave
characteristics of material particles.
– Therefore, in one equation deBroglie summarized the concepts
of waves and particles as they apply to low-mass, high-speed
objects.
– As a consequence of deBroglie’s discovery, we now have
techniques such as X-ray diffraction and electron microscopy to
study small objects. Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.5 Matter Waves
What is the wavelength of an electron moving with a speed of 5.97 × 106 m/s? The mass of the electron is
9.11 × 10–31 kg.

Solution
Analyze We are given the mass, m, and velocity, n, of the electron, and we must calculate its de Broglie
wavelength, l.

Plan The wavelength of a moving particle is given by Equation 6.8, so l is calculated by inserting the known
quantities h, m, and n. In doing so, however, we must pay attention to units.

Solve
Using the value of the Planck constant: h = 6.626 × 10–34 J-s

we have the following:

Comment By comparing this value with the wavelengths of electromagnetic radiation shown in Figure 6.4, we see
that the wavelength of this electron is about the same as that of X rays.

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Structure
of Atoms
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Sample Exercise 6.5 Matter Waves
Continued

Practice Exercise 1
Consider the following three moving objects: (i) a golf ball with a mass of 45.9 g moving at a speed of 50.0 m/s,
(ii) An electron moving at a speed of 3.50 × 105 m/s, (iii) A neutron moving at a speed of 2.3 × 102 m/s. List the three
objects in order from shortest to longest de Broglie wavelength.
(a) i < iii < ii (b) ii < iii < i (c) iii < ii < i (d) i < ii < iii (e) iii < i < ii

Practice Exercise 2
Calculate the velocity of a neutron whose de Broglie wavelength is 505 pm. The mass of a neutron is given in the table
inside the back cover of the text.

Electronic
Structure
of Atoms
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 The Uncertainty Principle

• Heisenberg showed that the more precisely the

momentum of a particle is known, the less precisely is its
position is known.
• We cannot determine the exact position, direction of
motion, and speed of subatomic particles simultaneously.
• For electrons: we cannot determine their momentum and
position simultaneously.
• ∆x = the uncertain in position; ∆mv = the uncertain in
momentum
h
(Dx) (Dmv) ³
4p Electronic
Structure
of Atoms
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 Quantum Mechanics

• Schrödinger proposed an equation containing both

wave and particle terms.
• Solving the equation leads to wave functions, ψ(PSI).
• The wave function describes the electron’s matter wave.
– The square of the wave function, ψ2, gives the probability of
finding the electron.
– That is, ψ2 gives the electron density for the atom.
• ψ2 is called the probability density.

• Electron density is another way of expressing probability.

– A region of high electron density is one where there is a high
probability of finding an electron.

Electronic
Structure
of Atoms
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 Quantum Mechanics

• The wave equation is

designated with a lowercase
Greek psi (y).
• The square of the wave
equation, y2, gives a
probability density map of
where an electron has a
certain statistical likelihood
of being at any given instant
in time.
Electronic
Structure
of Atoms
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 Orbitals and Quantum Numbers
• If we solve the Schrödinger equation, we get wave
functions and energies for the wave functions.
• We call ψ orbitals.
• Schrödinger’s equation requires three quantum
numbers:
• Principal quantum number, n. This is the same as
Bohr’s n.
– As n becomes larger, the atom becomes larger and the
electron is further from the nucleus.
– The n describes the energy level on which the orbital
resides.
– The values of n are integers ≥ 1. Electronic
Structure
of Atoms
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Angular Momentum Quantum Number (l)

• This quantum number depends on the value of

n.
• The values of l begin at 0 and increase to n – 1.
• We usually use letters for l (s, p, d and f for l =
0, 1, 2, and 3). Usually we refer to the s, p, d
and f orbitals.
• This quantum number defines the shape of the
orbital.

Electronic
Structure
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 Magnetic Quantum Number (ml)

• Magnetic quantum numbers give the three-

dimensional orientation of each orbital.
• The magnetic quantum number has integer
values between –l and +l.
– There are (2l+1) possible values of ml.
– For example, for l = 1, there are (2×1+1) = 3 values
of ml : 0, +1, and -1.
– Consequently, for l = 1, there are 3 orbitals: px, py
and pz.

Electronic
Structure
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 Magnetic Quantum Number (ml)
• A collection of orbitals with the same value of n is
called an electron shell.
– There are n2 orbitals in a shell described by a the n value.
• A set of orbitals with the same n and l is called a
subshell.
– Each subshell is designated by a number and a letter; 3p
• For example, 3p orbitals have n = 3 and l = 1.
– There are n types of subshells in a shell described by a
the n value;
• For example, for n = 3, there are 3 subshells: 3s, 3p
and 3d.
Electronic
Structure
of Atoms
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 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
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 s Orbitals

• All s orbitals are spherical.

• As n increases, the s orbitals get larger.
• As n increases, the number of nodes increases.
– A node is a region in space where the probability of finding
an electron is zero.
– ψ2 = 0 at a node.
– For an s orbital, the number of nodes is given by n – 1.
• We can plot a curve of radial probability density vs.
distance (r) from the nucleus.
– This curve is the radial probability function for the
orbital.
Electronic
Structure
of Atoms
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 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
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 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.
ψ2 is probability or electron density Electronic
Structure
Probability density [y(r)]2 of Atoms
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 p Orbitals

• There are three p orbitals: px, py and pz.

– The three p orbitals lie along the x-, y-, and z-axes of
a Cartesian system.
– The letters correspond to allowed values of ml of –1,
0, and +1.
• The orbitals are dumbbell shaped; each has
two lobes.
• As n increases, the p orbitals get larger.
• All p orbitals have a node at the nucleus.
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Structure
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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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Structure
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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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Structure
of Atoms
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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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Structure
of Atoms
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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.

Electronic
Structure
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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.)
Electronic
Structure
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 Electron Spin and
the Pauli Exclusion Principle
• Line spectra of many electron atoms show each line as
a closely spaced pair of lines.
• Stern and Gerlach designed an experiment to
determine why.
– A beam of atoms was passed through a slit and into a magnetic
field and the atoms were then detected.
– Two spots were found: one with the electrons spinning in one
direction and one with the electrons spinning in the opposite
direction.
• Since electron spin (electron as a tiny sphere spinning
on its own axis) is quantized,
– We define ms = spin magnetic quantum number = ± 1/2.
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Structure
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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© 2012 Pearson Education, Inc.
field, which affects its
energy.

Electronic
Structure
of Atoms
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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
two allowed values, +½ and –½.
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Structure
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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.

Electronic
Structure
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 Pauli Exclusion Principle

• Pauli’s exclusion
principle states that no
two electrons can have
the same set of 4
quantum numbers.
• Therefore, two electrons
in the same orbital must
have opposite spins.

Electronic
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 Electron Configurations
• Electron configurations tell us how the electrons are
distributed among the various orbitals of an atom.
• The most stable configuration, or ground state, is that in
which the electrons are in the lowest possible energy state.
• When writing ground-state electronic configurations:
– electrons fill orbitals in order of increasing energy with no more
than two electrons per orbital.
– no two electrons can fill one orbital with the same spin (Pauli).
– for degenerate orbitals, electrons fill each orbital singly before
any orbital gets a second electron: Hund’s rule
– How do we show spin?
• An arrow pointing upwards has ms = + 1/2 (spin up).
• An arrow pointing downwards has ms = – 1/2 (spin down).
Electronic
Structure
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 Electron Configurations

• This term shows the distribution of all electrons in

an atom.
• Each component consists of
– a number denoting the energy level;

4p5
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Structure
of Atoms
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 Electron Configurations

• This term shows the distribution of all electrons in

an atom
• Each component consists of
– a number denoting the energy level;
– a letter denoting the type of orbital;

4p5
Electronic
Structure
of Atoms
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 Electron Configurations

• This term shows the distribution of all electrons in

an atom.
• 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 Electronic
Structure
of Atoms
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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.
Electronic
Structure
of Atoms
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 Hund’s Rule

• Hund’s rule: for degenerate orbitals, the

lowest energy is attained when the number of
electrons with the same spin is maximized.
• Thus, electrons fill each orbital singly with
their spins parallel before any orbital gets a
second electron.
• By placing electrons in different orbitals,
electron-electron repulsions are minimized.

Electronic
Structure
of Atoms
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 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.
Sample Exercise 6.6 Subshells of the Hydrogen Atom
(a) Without referring to Table 6.2, predict the number of subshells in the fourth shell, that is, for n = 4. (b) Give the
label for each of these subshells. (c) How many orbitals are in each of these subshells?

Solution
Analyze and Plan We are given the value of the principal quantum number, n. We need to determine the allowed values
of l and ml for this given value of n and then count the number of orbitals in each subshell.

Solve There are four subshells in the fourth shell, corresponding to the four possible values of l (0, 1, 2, and 3).

These subshells are labeled 4s, 4p, 4d, and 4f. The number given in the designation of a subshell is the principal quantum
number, n; the letter designates the value of the angular momentum quantum number, l: for l = 0, s; for l = 1, p; for l = 2,
d; for l = 3, f.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.6 Subshells of the Hydrogen Atom
Continued

There is one 4s orbital (when l = 0, there is only one possible value of ml: 0). There are three 4p orbitals (when l = 1,
there are three possible values of ml: 1, 0, –1). There are five 4d orbitals (when l = 2, there are five allowed values of
ml: 2, 1, 0, –1, –2). There are seven 4f orbitals (when l = 3, there are seven permitted values of ml: 3, 2, 1, 0, –1, –2, –3).

Practice Exercise 1
An orbital has n = 4 and ml = –1. What are the possible values of l for this orbital?
(a) 0, 1, 2, 3 (b) –3, –2, –1, 0, 1, 2, 3 (c) 1, 2, 3 (d) –3, –2 (e) 1, 2, 3, 4

Practice Exercise 2
(a) What is the designation for the subshell with n = 5 and l = 1? (b) How many orbitals are in this subshell?
(c) Indicate the values of ml for each of these orbitals.

Electronic
Structure
of Atoms
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Condensed Electron Configurations
• Electron configurations may be written using a
shorthand notation (condensed electron
configuration):
– Write the valence electrons explicitly; Valence electrons
are electrons in the outer shell. These electrons are gained
and lost in reactions.
– Write the core electrons corresponding to the filled noble
gas in square brackets; Core electrons are electrons in the
inner shells. These are generally not involved in bonding.
• Example:
– P is 1s22s22p63s23p3,
– but Ne is 1s22s22p6.
– Therefore, P is [Ne]3s23p3. 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; Sc to Zn, 10
elements
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 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 (rare earth elements,
atomic numbers 57 to 70) have electrons entering
the 4f sublevel; Ce(Cerium) – Lu(Lutetium)
• The actinide elements (including Uranium, at.
no. 92, and Plutonium, at. no. 94) have electrons
entering the 5f sublevel; Th(Thorium) –
Lr(Lawrencium)
– The actinide elements are radioactive and most are not
found 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)

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Periodic Table
• Groups 1A and 2A have their s orbitals being filled.
• Groups 3A–8A have their p orbitals being filled.
• The s-block and p-block of the periodic table contain the
representative, or main-group, elements.
• Groups 3B–2B have their d orbitals being filled.
• The lanthanides and actinides have their f orbitals being
filled.

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.
• Note that the 3d orbitals fill after the 4s orbital.
Similarly, the 4f orbitals fill after the 5d orbitals.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Periodic Table and
Electron Configuration
• In general, for representative elements we do not
consider the electrons in completely filled d or f subshells
to be valence electrons.
• In general, for transition elements we do not consider the
electrons in a completely filled f subshell to be valence
electrons.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
 Order of Orbital Filling
• When the np orbitals are full, the next orbital is the
(n+1)s orbital instead of nd or nf orbitals
– The n=1 and 2 electron screen the nd or nf
orbitals more effectively than they screen the
(n+1)s orbital (전자구름의 모양 때문)

Electronic
Structure
74 of Atoms
© 2018 Pearson Education, Inc.
 Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.7 Orbital Diagrams and Electron Configurations
Draw the orbital diagram for the electron configuration of oxygen, atomic number 8. How many unpaired electrons
does an oxygen atom possess?

Solution
Analyze and Plan Because oxygen has an atomic number of 8, each
oxygen atom has eight electrons. Figure 6.25 shows the ordering of
orbitals. The electrons (represented as half arrows) are placed in the
orbitals (represented as boxes) beginning with the lowest-energy
orbital, the 1s. Each orbital can hold a maximum of two electrons
(the Pauli exclusion principle). Because the 2p orbitals are
degenerate, we place one electron in each of these orbitals (spin-up)
before pairing any electrons (Hund’s rule).

Solve Two electrons each go into the 1s and 2s orbitals with their
spins paired. This leaves four electrons for the three degenerate
2p orbitals. Following Hund’s rule, we put one electron into each
2p orbital until all three orbitals have one electron each. The fourth
electron is then paired up with one of the three electrons already in a
2p orbital, so that the orbital diagram is

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.7 Orbital Diagrams and Electron Configurations
Continued

The corresponding electron configuration is written 1s22s22p4. The atom has two unpaired electrons.

Practice Exercise 1
How many of the elements in the second row of the periodic table (Li through Ne) will have at least one unpaired
electron in their electron configurations?
(a) 3 (b) 4 (c) 5 (d) 6 (e) 7

Practice Exercise 2
(a) Write the electron configuration for silicon, element 14, in its ground state. (b) How many unpaired electrons does
a ground-state silicon atom possess?

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.8 Electron Configurations for a Group
What is the characteristic valence electron configuration of the group 7A elements, the halogens?

Solution
Analyze and Plan We first locate the halogens in the periodic table, write the electron configurations for the first two
elements, and then determine the general similarity between the configurations.

Solve The first member of the halogen group is fluorine (F, element 9). Moving backward from F, we find that the
noble-gas core is [He]. Moving from He to the element of next higher atomic number brings us to Li, element 3.
Because Li is in the second period of the s block, we add electrons to the 2s subshell. Moving across this block gives
2s2. Continuing to move to the right, we enter the p block. Counting the squares to F gives 2p5. Thus, the condensed
electron configuration for fluorine is

The electron configuration for chlorine, the second halogen, is

From these two examples, we see that the characteristic valence electron configuration of a halogen is ns2np5, where n
ranges from 2 in the case of fluorine to 6 in the case of astatine.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.8 Electron Configurations for a Group
Continued

Practice Exercise 1
A certain atom has an ns2np6 electron configuration in its outermost occupied shell. Which of the following elements
could it be? (a) Be (b) Si (c) I (d) Kr (e) Rb

Practice Exercise 2
Which group of elements is characterized by an ns2np2 electron configuration in the outermost occupied shell?

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.9 Electron Configurations from the Periodic Table
(a) Based on its position in the periodic table, write the condensed electron configuration for bismuth, element 83.
(b) How many unpaired electrons does a bismuth atom have?

Solution
(a) Our first step is to write the noble-gas core. We do this by locating bismuth, element 83, in the periodic table. We
then move backward to the nearest noble gas, which is Xe, element 54. Thus, the noble-gas core is [Xe].

Next, we trace the path in order of increasing atomic numbers from Xe to Bi. Moving from Xe to Cs, element 55,
we find ourselves in period 6 of the s block. Knowing the block and the period identifies the subshell in which we
begin placing outer electrons, 6s. As we move through the s block, we add two electrons: 6s2.

As we move beyond the s block, from element 56 to element 57, the curved arrow below the periodic table reminds
us that we are entering the f block. The first row of the f block corresponds to the 4f subshell. As we move across
this block, we add 14 electrons: 4f 14.

With element 71, we move into the third row of the d block. Because the first row of the d block is 3d, the second
row is 4d and the third row is 5d. Thus, as we move through the ten elements of the d block, from element 71 to
element 80, we fill the 5d subshell with ten electrons: 5d10.

Moving from element 80 to element 81 puts us into the p block in the 6p subshell. (Remember that the principal
quantum number in the p block is the same as that in the s block.) Moving across to Bi requires three electrons:
6p3. The path we have taken is Putting the parts together, we obtain the condensed electron configuration:
[Xe]6s24f 145d106p3. This configuration can also be written with the subshells arranged in order of increasing
principal quantum number: [Xe]4f 145d106s26p3.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.9 Electron Configurations from the Periodic Table
Continued

Finally, we check our result to see if the number of electrons equals the atomic number of Bi, 83: Because Xe has
54 electrons (its atomic number), we have 54 + 2 + 14 + 10 + 3 = 83. (If we had 14 electrons too few, we would
realize that we have missed the f block.)

(b) We see from the condensed electron configuration that the only partially occupied subshell is 6p. The orbital
diagram representation for this subshell is

In accordance with Hund’s rule, the three 6p electrons occupy the three 6p orbitals singly, with their spins parallel.
Thus, there are three unpaired electrons in the bismuth atom.
Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.
Sample Exercise 6.9 Electron Configurations from the Periodic Table
Continued

Practice Exercise 1
A certain atom has a [noble gas]5s24d105p4 electron configuration. Which element is it?
(a) Cd (b) Te (c) Sm (d) Hg (e) More information is needed

Practice Exercise 2
Use the periodic table to write the condensed electron configuration for (a) Co (element 27), (b) In (element 49).

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.
 Anomalous Electron Configurations

• There are many elements that appear to

violate the electron configuration guidelines.
– Examples:
• Chromium is [Ar]3d54s1 instead of [Ar]3d44s2.
• Copper is [Ar]3d104s1 instead of [Ar]3d94s2.
– Half-full (d5) and full (d10) d subshells are
particularly stable.

Electronic
Structure
of Atoms
© 2018 Pearson Education, Inc.