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Chapter 7

Quantum Theory and the

Electronic Structure of Atoms

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 Properties of waves
Quantum theory enables us to predict and understand the critical
role that electrons play in chemistry.

Wavelength (λ) is the distance between identical points on successive waves.

Amplitude is the vertical distance from the midline of a wave to the peak or trough.
Frequency (ν) is the number of waves that pass through a particular point in 1 second
(Hz = 1 cycle/s).

The speed (u) of the wave = λ × ν

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 Light as a wave
Maxwell (1873), proposed that visible light consists of
electromagnetic waves.

Electromagnetic radiation is the

emission and transmission of
energy in the form of
electromagnetic waves.

Speed of light (c) in vacuum = 3.00  10 m / s

8

All electromagnetic radiation

λ×ν=c
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 Electromagnetic spectrum

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 Mystery #1, “heated solids problem” solved by
Planck in 1900
When solids are heated, they emit electromagnetic radiation over
a wide range of wavelengths.

Radiant energy emitted by an object at a certain temperature

depends on its wavelength.

Planck: Energy (light) is emitted or absorbed in discrete units

(quantum).

Quantum to the smallest quantity of energy that can be emitted

(or absorbed) in the form of electromagnetic radiation.
𝒄
E=h×v 𝑬= 𝒉
𝝀
Planck’s constant (h) = 6.63 x 10-34 J.s
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 Mystery #2, “photoelectric effect” solved by
Einstein in 1905
The photoelectric effect, a phenomenon in which electrons are
ejected from the surface of certain metals exposed to light of at
least a certain minimum frequency, called the threshold frequency

Light has both:

1) wave nature
2) particle nature

Photon is a “particle” of light

h v = KE + W
KE = h v − W
where W is the work function and depends how
strongly electrons are held in the metal.

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 Line Emission spectrum of hydrogen atoms

• The four lines, of the hydrogen atom, that appear are all in the visible region,
because the photographic plate only detects visible light.
• The line at 410 nm appears violet, and the line at 434 nm appears blue. The
emission line at 486 nm appears blue-green, and the line at 656 nm appears red.

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 Emission spectra of some elements
hydrogen (4 lines) sodium (1 line), barium (20 lines) and calcium (14 lines) etc..

• Every element has a unique

emission spectrum.

• The characteristic lines in

atomic spectra can be used in
chemical analysis to identify
unknown atoms, much as
fingerprints are used to identify
people.

• When the lines of the

emission spectrum of a known
element exactly match the lines
of the emission spectrum of an
unknown sample, the identity
of the sample is established.

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 Bohr’s model of the atom (1913)
The energy of the photon is equal to the energy difference between
the two n levels in the atom.

1. e– can only have specific (quantized) energy values.

2. light is emitted as e moves from one energy level to a lower
energy level
3. The radius of each circular orbit depends on n2
4. e– is allowed to occupy orbits with energies as:

 1 
En = − RH  2 
n 
n (principle quantum number) = 1, 2, 3, .
RH ( Rydberg constant ) = 2.18  10 −18 J

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 Quantized energy

• When an electron undergoes a

transition, it can only exist in an
energy level, not between energy
levels, because energy levels of
the atom are quantized.

• A way to think about this is a ball

on a staircase. The ball can only
rest on steps, not between steps,
much like how an electron can only
exist in an energy level, not
between energy levels.

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 Energy transitions of the hydrogen atom
Ephoton = ΔE = Ef − Ei
 1 
E f = − RH  2 
n
 f 
 1 
Ei = − RH  2 
 ni 
 1 1 
ΔE = RH  2 − 2 
n n 
 i f 
ni = initial orbit and nf = final orbit

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 Hydrogen atom emission series

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 (Continue..)

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 Quantization of electron energy

Why is e– energy quantized?

De Broglie (1924) reasoned

that e– is both particle and
wave.
h
2π r = nλ λ=
−
mu
u = velocity of e
m = mass of e −
(a) The circumference of the orbit is equal to an
integral number of wavelengths. This is an
2 𝜋 r = circumference of allowed orbit.
the allowed orbit (b) The circumference of the orbit is not equal to
an integral number of wavelengths. As a result,
the electron wave does not close in on itself.
This is a nonallowed orbit.
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 Schrodinger wave equation

In 1926 Schrodinger wrote an equation that described both

the particle and wave nature of the e–
Wave function ( ) describes:
1. energy of e– with a with a given 
2. probability of finding e– in a volume of space

Schrodinger’s equation can only be

solved exactly for the hydrogen atom
Must approximate its solution for
multi electron systems.

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  is a function of four numbers called
quantum numbers
( n , l, ml , ms )
Principal Quantum Number n
n = 1, 2, 3, 4, .

distance of e– from the nucleus

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 quantum numbers : ( n, l, ml , ms )
Angular Momentum Quantum Number l

The shape of the “volume” of space that the e- occupies

for a given value of n, l = 0, 1, 2, 3, … n - 1

n = 1, l = 0 l=0 s orbital
n = 2, l = 0 or 1 l=1 p orbital
n = 3, l = 0, 1, or 2 l=2 d orbital
n = 4, l = 0, 1, 2, or 3 l=3 f orbital

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 l = 0 (s orbitals)

l = 1 (p orbitals)

l = 2 (d orbitals)

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 quantum numbers : ( n, l, ml , ms )

Magnetic Quantum Number ml

for a given value of l

ml = −l , ., 0, . + l

If l = 1 (p orbital), ml = −1, 0, or + 1

If l = 2 (d orbital), ml = -2, -1, 0, +1, +2

orientation of the orbital in space

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 ml = -1, 0, or 1 3 orientations in space

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 ml = -2, -1, 0, 1, or 2 5 orientations in space

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 ( n, l, ml , m s )
Spin Quantum Number m S
1 1
ms = + or −
2 2

1 1
ms = + ms = −
2 2

An electron that spins counterclockwise is given a spin value of

−1/2. These electrons, known as "spin down", are indicated by an
arrow pointing downward.

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 Quantum numbers: (n, l, ml, ms)
Existence (and energy) of electron in atom is described by
its unique wave function 

Pauli exclusion principle - no two electrons in an atom

can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8)

Each seat can hold only one individual at a
time.

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 Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

How many electrons can an orbital hold?

If n, l, and ml are fixed, then ms = ½ or - ½

 = (n, l, ml, ½) or  = (n, l, ml, -½)

An orbital can hold 2 electrons

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 How many 2p orbitals are there in an atom?
n=2 If l = 1, then ml = -1, 0, or +1
2p 3 orbitals

l=1

How many electrons can be placed in the 3d subshell?

n=3 If l = 2, then ml = -2, -1, 0, +1, or +2

3d 5 orbitals which can hold a total of 10 e–

l=2

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 Paramagnetism and Diamagnetism

Paramagnetic Diamagnetic
unpaired electrons all electrons paired

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 The energies of orbitals
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

n=1

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 Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l=2

n=3 l=1
n=3 l=0

n=2 l=1
n=2 l=0

n=1 l=0

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 Aufbau principle
“Fill up” electrons in lowest energy orbitals (Aufbau principle)

? ?

C 6 e-
B 5 e- 1s22s22p1
Be 4 e- 1s22s2
Li 3 e- 1s22s1
He 2 e- 1s2
H 1 e- 1s1

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 Hund’s rule
The most stable arrangement of electrons in subshells is the one
with the greatest number of parallel spins (Hund’s rule).

? ? ?

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The most stable arrangement of electrons in subshells is the one
with the greatest number of parallel spins (Hund’s rule).

Ne 10 e- 1s22s22p6
F 9 e- 1s22s22p5
O 8 e- 1s22s22p4
N 7 e- 1s22s22p3
C 6 e- 1s22s22p2

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 Aufbau principle + Hund’s rule

Ne 10 e- 1s22s22p6
F 9 e- 1s22s22p5
O 8 e- 1s22s22p4
N 7 e- 1s22s22p3
C 6 e- 1s22s22p2
B 5 e- 1s22s22p1
Be 4 e- 1s22s2
Li 3 e- 1s22s1
He 2 e- 1s2
H 1 e- 1s1

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 Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
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 Electron configuration is how the electrons are
distributed among the various atomic orbitals in an atom.

number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram
H
1s1
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 Outermost subshell being filled with electrons

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 What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the last

(outermost) electron in Cl?
Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital
n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½

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 Example 7.12
An oxygen atom has a total of eight electrons. Write the four quantum
numbers for each of the eight electrons in the ground state.

Strategy
We start with n = 1 and proceed to fill orbitals in the order
shown in Figure 7.24.

For each value of n we determine the possible values of l.

For each value of l, we assign the possible values of ml.

We can place electrons in the orbitals according to the Pauli

exclusion principle and Hund’s rule.

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 Solution
We start with n = 1, so l = 0, a subshell corresponding to the 1s orbital. This orbital
can accommodate a total of two electrons.
Next, n = 2, and l may be either 0 or 1. The l = 0 subshell contains one 2s orbital,
which can accommodate two electrons. The remaining four electrons are placed
in the l = 1 subshell, which contains three 2p orbitals. The orbital diagram is

The results are summarized in the following table:

Of course, the placement of the eighth

electron in the orbital labeled ml = 1
is completely arbitrary. It would be equally
correct to assign it to ml = 0 or ml = -1.

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 Ground state electron configurations

Table 7.3 The Ground-State

Electron Configurations of
the Elements*

Access the text alternative for

slide images.

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 Example 7.13
Write the ground-state electron configurations for
(a) sulfur (S)
(b) palladium (Pd), which is diamagnetic

(a) Strategy
How many electrons are in the S (Z = 16) atom? We start with n = 1 and
proceed to fill orbitals in the order shown in Figure. For each value of
l, we assign the possible values of ml. We can place electrons in the orbitals according to
the Pauli exclusion principle and Hund’s rule and then write the electron configuration.
The task is simplified if we use the noble-gas core preceding S for the inner electrons.

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 Solution
Sulfur has 16 electrons. The noble gas core in this case is [Ne]. (Ne is the noble
gas in the period preceding sulfur.) [Ne] represents 1s 2 2 s 2 2 p6 .

This leaves us 6 electrons to fill the 3s subshell and partially fill the 3p subshell.
Thus, the electron configuration of S is
1s 2 2 s 2 2 p6 3s 2 3 p 4 or  Ne  3s 2 3 p 4 .
(b) Strategy
We use the same approach as that in (a). What does it mean to say that Pd is a
diamagnetic element?

Solution
Palladium has 46 electrons. The noble-gas core in this case is [Kr]. (Kr is the
noble gas in the period preceding palladium.) [Kr] represents
1s 2 2 s 2 2 p6 3s 2 3 p 6 4 s 2 3d 10 4 p 6
The remaining 10 electrons are distributed among the 4d and 5s orbitals. The
three choices are
(1) 4d , ( 2 ) 4d
10 9 1
5s , and ( 3) 4d 5s .
8 2

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 Because palladium is diamagnetic, all the electrons are paired and its
electron configuration must be

1s 2 2 s 2 2 p6 3s 2 3 p 6 4 s 2 3d 10 4 p 6 4d 10

or simply  Kr  4d 10 . The configurations in (2) and (3) both represent

paramagnetic elements.

Check
To confirm the answer, write the orbital diagrams for (1), (2), and (3).

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