2 STUDY UNIT 2

Quantum mechanics and periodicity

2

2.1 A brief introduction to quantum chemistry

2.2 Quantum numbers and atomic orbitals
2.3 Atomic properties and periodic trends
2.4 Electron configurations
2.5 Ions
2.6 Noble gas core notation
2.7 Subshell energies in a multi-electron atom
2.8 Effective nuclear charge

LEARNING OUTCOMES

When you have completed this study unit, you should be able to do the following:

• Distinguish between orbits and orbitals.

• Draw and identify the characteristic shapes of s and p orbitals.
• Define the quantum numbers and relate them to the position of an electron.
• Determine the nuclear and effective nuclear charge of an atom.
• Predict trends in atomic radii, electronegativity, ionisation energy and electron
affinity.
• Compare properties of atoms based on their position on the periodic table.
• Construct electron configurations for atoms and ions, and compare them with
the noble gas configuration.
• Construct subshell energies for atoms and ions.
• Distinguish between core and valence electrons, and calculate effective nuclear
charge.

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 2.1 A BRIEF INTRODUCTION TO QUANTUM CHEMISTRY
In order to study the electronic structure of the atom we need to analyse the
electromagnetic radiation that is emitted by an excited atom. This radiation
is characterised by its wavelength, O (lamda), and frequency, Q (nu). These
quantities are related to the speed of light c, where c = OQ.

Max Planck has found that the vibrational energies of atoms are quantised,
which means the possible energies a vibrating atom can have are limited to
certain values or quanta according to the equation:

E = nhQ, where n = 1, 2, 3 ... etc.

The value of n (called quantum number) must be a whole number, and h is

Planck’s constant.

Albert Einstein has shown that light consists of particles (photons), each with
an energy E = hQ. According to Niels Bohr, an electron in an atom has energy
levels and when an electron in a higher energy level drops to a lower level,
a photon is emitted. For a particle which has a mass of (m) and a velocity of
(Q), the wavelength is related to momentum (mQ) by the De Broglie relation.
The wave properties of a particle are described by a wave function < (psi).
The wave function and its square, <2, provide values for all particle locations
around a nucleus. From the wave function we can determine the probability
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8 Ac tivit y 2.1
1. How are the wavelength and the frequency of an electromagnetic
wave related?
2. Briefly describe the regions of the electromagnetic spectrum, starting
with the shortest wavelengths and progressing to longer wavelengths.
3. What is the frequency of light with a wavelength of 465 nm? (Note
that this corresponds to the blue region of the visible spectrum.)

2.2 QUANTUM NUMBERS AND ATOMIC ORBITALS

2.2.1 Bohr’s atomic model

In 1913, Niels Bohr proposed a model of an atom based on Planck’s quantum
theory of radiation. The basic postulates of Bohr’s theory are the following:

• An atom consists of a small, positively charged nucleus around which

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• 6JGUGQTDKVUCTGCUUQEKCVGFYKVJFGſPKVGGPGTIKGUECNNGFGPGTI[UJGNNU6JG[
are designated as K, L, M, N, ... shells, or numbered 1, 2, 3, 4, … from the
nucleus outward.
• As long as the electron remains in a particular energy shell, its energy
remains constant.

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 S T U DY U N I T 2: Q u a n t u m m e c h a n i c s a n d p e r i o d i c i t y

• Only those orbits are permitted in which angular momentum of the electron
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Study Bohr’s postulates, which account for the stability of the H atom and
for its spectrum, from the textbook. The postulates lead to the concepts of
energy levels of electrons in atoms and the transition of electrons between
energy levels.

2.2.2 Quantum numbers

In this section we look at how to use quantum numbers to describe an electron
in an atom. There are different clouds of probability or orbitals where electrons
ECPQEEWTCTQWPFCPCVQO6JGſTUVQPGKUECNNGFCPs orbital, the second a p
orbital, then a d orbital, an f orbital and so on. What do these orbitals look
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Each electron in an atom is characterised by four different quantum numbers.

The distribution of an electron in space, in other words its atomic orbital,
is characterised by three of these quantum numbers, namely the principal
quantum number, the angular momentum quantum number (also called
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quantum number (the spin quantum number) describes the spin of the electron
and hence its magnetic properties.

More details about these numbers are given below. Study the general meaning
of these numbers and their appropriate allowed values in detail.

Principal quantum number (n)

The principal quantum number (n) determines the main energy shell or energy
level in which the electron is present. This number is related to size: the larger
the number n gets, the larger the area in which electrons would probably be
found.

The principal quantum number gives the average distance of the electron from
the nucleus and the energy associated with it. Allowed values for n are whole
number values 1, 2, 3, 4 and so on.

Azimuthal quantum number or angular quantum number (ℓ)

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electron. This describes the sublevel or subshell in a given principal energy
shell to which the electron belongs. Allowed values for ℓ can only be positive
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number.

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 Magnetic quantum number (mℓ)

The magnetic quantum number (mℓ) describes the spatial orientation of the
orbital in which the electron is found. Orbitals that have the same n and ℓ
values are called degenerate orbitals. The magnetic quantum number allows
us to distinguish between orbitals that have the same energy. Allowed values
for mℓ can only be integral values from -ℓ to +ℓ, including 0.

Remember, each orbital can take 2 electrons, so a p orbital with 3 orientations

actually has 3 p orbitals available and thus can contain 6 electrons (2 in each
orbital).

Spin quantum number (ms)

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is called spin. The orientation of spin of an electron is indicated by its spin
quantum number ms. Allowed values for ms can only be two values, namely
+½ (clockwise spin) or -½ (anticlockwise spin).

9 Ac tivit y 2. 2
1. Which of the following sets of quantum numbers are valid?
If the set is invalid, explain why it is invalid.

(i) n = 3, ℓ = 3, ml = -2, ms = +½
(ii) n = 1, ℓ = 0, ml = 1, ms = -½
(iii) n = 4, ℓ = 3, ml = -3, ms = -½

2. Draw the general shape of the following orbitals:

(i) s orbital
(ii) p orbital

3. How many orbitals are there in a subshell for which n = 4 and

ℓ = 3?

2.2.3 Shapes of atomic orbitals

In this section the shapes of atomic orbitals are described. Study the shape of
the s orbital and p orbitals carefully and make sure that you understand the
various orbital orientations and probability distributions.

An atomic orbital is the space around the nucleus in which there is a high
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CPGNGEVTQPFGETGCUGUYKVJFKUVCPEG DWVFQGUPQVDGEQOG\GTQ FTCYKPI
boundary surfaces is the method generally used to show the shape of an orbital.
Boundary surfaces enclose 95–99% of the probability of locating an electron.

NOTE: In this course you are expected to know only the shapes of the s orbital
and the p orbital.
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 S T U DY U N I T 2: Q u a n t u m m e c h a n i c s a n d p e r i o d i c i t y

2.3 ATOMIC PROPERTIES AND PERIODIC TRENDS

Since elements in the same group of the periodic table have similar valence
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behaviour (the relative description of properties across the periodic table). In
order to understand the periodicity of properties it is necessary to correlate
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position in the periodic table.

In this section we look at four physical properties of an atom, namely atomic

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show distinct periodic behaviour and determine the chemical characteristics
of an element.

2.3.1 Atomic radius

The effective nuclear charge felt by the outer electrons of the atoms in a group
on the periodic table is nearly constant. However, the principal quantum
number n increases and the orbitals become larger from top to bottom within
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The principal quantum number n is the same across the period. However,
the effective nuclear charge increases. This causes the negatively charged
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to right across a period.

To summarise: Atomic radius decreases from left to right in a period and

increases from top to bottom in a group.

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FKUEWUUGFKPVJGRCTCITCRJUCDQXG6JGCFFKVKQPCNGHHGEVQPUK\GKUECWUGF
by the addition or removal of electrons from the neutral atom. Negative ions
(anions) are larger than the neutral atom because the extra electrons cause
more electron repulsion, which increases the volume of the electron cloud.
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of the electron cloud is smaller than that of the neutral atom.

2.3.2 Electronegativity
Electronegativity is a measure of the ability of an atom to attract the shared
electrons to itself when bonded to another atom in a molecule. The Pauling
scale is most commonly used to measure electronegativity. Fluorine (the most
electronegative element) is assigned a value of 4.0, and values range down to
caesium and francium, which are the least electronegative at 0.7. The lighter
noble gases (He, Ne, Ar) are not electronegative as they have fully occupied
orbitals and do not form bonds. As the atomic radius decreases, the nuclear
forces of attraction increase and so does electronegativity.

To summarise: Electronegativity increases from left to right across a period,

and it decreases down a group.

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 2.3.3 Ionisation energy
Ionisation energy is required to remove the outermost or highest energy
level electron from a neutral atom in the gas phase. Ionisation energies vary
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ionisation energy can all be explained in terms of the structures of the atoms
involved.

Note that atoms with more than one electron have an ionisation energy (IE)
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energy, because it is the energy to remove one of the outer (valence) electrons.
The ionisation energy for each electron that is left increases, because more
energy is needed to remove another e - from a more positive ion. For example,
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520 kJ.mol-1; the second IE is 7 297 kJ.mol-1; and the third IE is 11 810 kJ.mol-1.

As the quantum number n increases down the group, the IE decreases because
the electrons are further from the nucleus and are bound less tightly. On the
other hand, the effective nuclear charge increases from left to right across a
period, and the IE increases.

To summarise: Ionisation energy tends to increase as the atomic number

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in ionisation energy as the atomic number increases. Metals typically have
a low ionisation energy, whereas non-metals have a high ionisation energy.

2.3.4 Electron affinity

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neutral atom in the gas phase gains an electron to form a negatively charged
ion. When an electron is added to a gaseous neutral atom, energy is released
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given a negative value. If an electron must be forced into an atom or ion, energy
must be added (i.e. the reaction is endothermic) and the EA is positive. Metals
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To summarise: The general trend down a column or group is a decreasing

tendency to gain electrons. Across a period, there is an increasing tendency
for atoms to attract electrons.

10 Ac tivit y 2. 3
Answer the following questions and briefly explain each answer:

(i) Rank the following in order of increasing atomic radius: O, S and F.

(ii) Which has the largest ionisation energy: P, Si, S or Se?
(iii) Place the following in order of increasing radius: O2-, N3- or F-.
(iv) Place the following in order of increasing ionisation energy: Cs, Sr, Ba.

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 S T U DY U N I T 2: Q u a n t u m m e c h a n i c s a n d p e r i o d i c i t y

2.4 ELECTRON CONFIGURATIONS

The electronic structures of atoms and the periodicity of the elements are
very important parts of your study of chemistry. It is necessary to know the
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the similarities between the members of a group of elements. In this section
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the period and group numbers and the Aufbau principle. The distribution of
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number and its orbital, together with the number of electrons present in each
orbital as a superscript.

2.4.1 The Aufbau principle

The Aufbau principle states that the electrons in an atom are arranged so that
they occupy orbitals in order of their increasing energy. According to this
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electrons must then be placed into the orbital with the next highest energy.

FIGURE 2.1
Empty orbitals versus relative energies

2.4.2 Hund’s rule

Hund’s rule states that when degenerate orbitals (orbitals of the same energy)
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before pairing.

2.4.3 Pauli’s exclusion principle

Pauli’s exclusion principle states that no two electrons in an atom can have the
same four quantum numbers. This means that each orbital can accommodate
a maximum of two electrons only if they have opposite spins.

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 2.5 IONS
An ion is a charged species formed through either the loss or the gain of
an electron or electrons. A neutral atom (an atom with an equal number of
protons and electrons) may lose an electron or electrons to become a positively
charged ion, called a cation. When a hydrogen atom loses its single electron,
it remains with only a proton in the nucleus and it thus becomes positively
charged. A positively charged hydrogen ion is equivalent to a proton, hence
it is called a proton.

Other atoms can lose one or more valence electrons to resemble the noble
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example, when sodium, Na (1s22s22p63s1) loses its single valence electron
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in number of electrons) with that of neon (1s22s22p6).

A neutral atom can also gain an electron or electrons to become a negatively

charged ion called an anion+HVJGCVQOICKPUUWHſEKGPVGNGEVTQPUVQſNNKVU
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(1s12s22p5) gains one electron to become isoelectronic with Ne (1s22s22p6).

11 Ac tivit y 2.4
1. Write down the electron configuration of a magnesium 2+ ion and
identify the noble gas with the same electron configuration.
2. For the ions: Al3+, S2- and Cl-:

(i) Show the electron configuration by means of an orbital – energy

diagram indicating the valence electrons.
(ii) Draw an electron-dot structure for each of the above ions, and
then arrange them in order of increasing size.

3. What is the valence shell electron configuration of the S atom?

4. Which orbital diagram below is allowed by the Pauli exclusion principle?
Give reasons for your choice.

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 S T U DY U N I T 2: Q u a n t u m m e c h a n i c s a n d p e r i o d i c i t y

2.6 NOBLE GAS CORE NOTATION

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cumbersome. The noble gas core notation can be used to abbreviate the core
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core electrons are indicated by the symbol of the equivalent noble gas in
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represented as [He] 2s22p4, where the notation [He] represents the core shell
electrons of oxygen, in other words those electrons closer to the nucleus which
are not involved in any chemical reaction. The remaining part of the electron
EQPſIWTCVKQP U22p4) represents the valence shell electrons. The noble gas
core notation for potassium (K) with 19 electrons (1s22s22p63s23p64s1) can be
represented as [Ar] 4s1.

12 Ac tivit y 2. 5
Use the noble gas core notation to draw the electron configurations for
P and Cl atoms.

2.7 SUBSHELL ENERGIES IN A MULTI-ELECTRON ATOM

According to quantum theory and the Bohr model, the energy of mono-electron
atoms (like H) depends on n only, whereas the energy level of multi-electron
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electrons are placed in orbitals or subshells in order of increasing energy.

There are two general rules that can be used to predict energy levels of subshells:

1. Electrons are assigned to subshells in order of increasing (n + l) value.

2. When two subshells have the same value of (n + l), electrons are assigned
ſTUVVQVJGUWDUJGNNQHNQYGTn.

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 Consider the following table regarding (n + l) for different subshells:

TABLE 2.1
The (n + l) for different subshells

Subshell n l n+l

4d 4 2 6

4p 4 1 5

4s 4 0 4

3d 3 2 5

3p 3 1 4

3s 3 0 3

2p 2 1 3

2s 2 0 2

1s 1 0 1

When we look at the 2p and 3s subshell, we see that the n + l values are the
same. Thus, the second rule of looking at n are considered to determine which
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is then: 1s, 2s, 2p, 3s, 3p, 4sFRF6JKUſNNKPIQTFGTKUUWOOCTKUGFWUKPI
VJGFKCIQPCNTWNG UGGſIWTG 

FIGURE 2.1
The diagonal rule

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 S T U DY U N I T 2: Q u a n t u m m e c h a n i c s a n d p e r i o d i c i t y

13 Sample exercise 2.1

Draw the subshell energy level diagram of Si.

Solution

3p
3s
2p
2s
1s
Si

14 Ac tivit y 2.6
1. Draw the subshell energy level diagrams of the following atoms and
ions:

(i) O
(ii) Mg2+
(iii) S
(iv) Cl-

2. What are the correct electron configurations for Cr and Cu? Consult
the textbook. Why are they different from what would be written
using the Aufbau principle?

2.8 EFFECTIVE NUCLEAR CHARGE

Read the section about effective nuclear charge in the textbook. You should
be able to explain what is meant by the following terms in your own words:

• core electrons
• valence electrons
• nuclear charge
• effective nuclear charge

Core electrons are the electrons closest to the nucleus of the atom. They
include all electrons except the electrons found in the outer shell (highest
energy level). These outer shell electrons are called the valence electrons.
The effective nuclear charge is the positive charge which the outer electron
experiences. It is less than the actual nuclear charge because the electrons
in the inner shells partially neutralise the actual nuclear charge. The Li atom,
HQTGZCORNGJCUCPGNGEVTQPKEEQPſIWTCVKQPQHU22s1. It has 3 protons (p+) in
the nucleus and 2e– in the inner shell (2 core electrons). The effective nuclear
charge experienced by the outer electron is therefore +1.

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 You can also use the following formula for calculating effective nuclear charge:

Zeff or Z* = Z – S

(Z is the number of protons in the nucleus and S is the number of core electrons.)

15 Sample exercise 2. 2
Answer the following questions on F:

(i) Write down the electron configuration for F.

(ii) How many core electrons does F have?
(iii) How many valence electrons does F have?
(iv) What is the Zeff which is experienced by the outer electrons?

Solution

(i) 1s2 2s2 2p5

(ii) 2 core electrons
(iii) Outer shell or energy level is 2. The electrons in the second shell is 7
(2 + 5).
(iv) Zeff = 9 – 2 = 7; thus the effective nuclear charge for F is +7.

16 Ac tivit y 2.7
How many core electrons and valence electrons do the following atoms
have? Also determine the effective nuclear charge experienced by the
outer electron.

(i) Mg
(ii) Si
(iii) O
(iv) Cl-

SUMMARY
In this study unit you learned about quantum chemistry, quantum numbers and
atomic orbitals. We looked at atomic properties and periodic trends, which
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gas core notation. Finally, we extended our understanding of periodic trends
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by an outer electron. Please return to the learning outcomes and make sure
that you have achieved them all.

In the following study unit we discuss chemical bonding and bonding theories.

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24