Atomic Structure of Matter

• Matter is composed of atoms.

– Atoms have a nucleus which contains

protons and neutrons.
– The nucleus is surrounded by a cloud of
electrons.
Fundamental Concepts of the Atom

• Two depictions of atomic structure. In both,

positive charged protons and neutral neutrons are
in the nucleus surrounded by negative charged
electrons.
Fundamental Concepts of the Atom
• Solar system depiction
of atomic structure.
–Emphasize proton,
neutron and electron
distribution, does not
accurately depict current
accepted model of
atomic structure.
Fundamental Concepts of the Atom
• Electrons are depicted
as clouds of negative
charge surrounding
the nucleus.
–The density of the small
dots is related to the
probability of finding an
electron at a particular
location.
Electrons, instead of traveling in defined orbits or hard, spherical “shells,” as
Bohr proposed, travel in diffuse
clouds around the nucleus .
Atomic Structure – The Quantum Mechanical Model

• The quantum mechanical model is based on quantum theory,

which says matter also has properties associated with waves.
According to quantum theory, it’s impossible to know the
exact position and momentum of an electron at the same
time. This is known as the Uncertainty Principle.
• The quantum mechanical model of the atom uses complex
shapes of orbitals (sometimes called electron clouds), volumes
of space in which there is likely to be an electron. So, this
model is based on probability rather than certainty.
The succeeding slides are the four quantum numbers,
showing how they are depicted and what aspects of
electrons they describe.

• The principal quantum number (n) describes the average

distance of the orbital from the nucleus — and the energy of the
electron in an atom.
It can have positive integer (whole number) values: 1, 2, 3, 4, and
so on. The larger the value of n, this means the electron has a
higher energy level and is less tightly bound to the nucleus.
The value of n defines the size.
 Quantum Numbers
• The principal quantum number, n, defines the
shell in which a particular orbital is found.

– n must be a positive integer

– n = 1 is the first shell, n = 2 is the second shell, etc.

– Each shell has different energies.

Quantum shells are also assigned
by a letter;
the shell n=1 is designated K,
for shell n= 2 is L,
for shell n= 3 is M,
and so on.
• Secondary quantum number or Azimuthal
quantum number (l)
- has values from 0 to n – 1. This defines the
shape of the orbital, and the value of l is
designated by the letters s, p, d, and f, which
correspond to values for l of 0, 1, 2, and 3.
In other words, if the value of l is 0, it is
expressed as s; if l = 1 = p, l = 2 = d,
and l = 3 = f
 Value of l (subshell) Letter
• Letter Designations of
the Subshells Value of l 0 s

(subshell)
1 p

2 d

3 f

4 g
 Quantum Numbers
• The energies of orbitals are specified
completely using only the n and l quantum
numbers.

– In magnetic fields, some emission lines split into

three, five, or seven components.

– A third quantum number describes splitting.

• Magnetic quantum number (ml) - Determines the
orientation of the orbital in space relative to the
other orbitals in the atom.
This quantum number has values from -l through 0 to
+l. For example, if the value of l = 1 (p orbital), you
can write three values for this number: –1, 0, and +1.
This means that there are three different p subshells
for a particular orbital.
The subshells have the same energy but different
orientations in space.
The total number of magnetic
quantum numbers for each l is 2l + 1.

For example, if l=2, there are 2(2)+1=5

magnetic quantum numbers with
values -2, -1, 0, +1, and +2.
 Quantum Numbers

• Note the relationship between number of

orbitals within s, p, d, and f and m .
l
Shape of an s orbital
Shape of the p orbitals
Shape of the d orbitals
• The spin quantum number, ms, determines the
number of electrons that can occupy an
orbital.

– ms = ±1/2

– Electrons described as “spin up” or “spin down”.

– An electron is specified by a set of four quantum

numbers.
Fourth Quantum Number, ms

• Associated with the electron spin

– Two spins are possible, clockwise or counterclockwise
– Values of ms, +½, and −½

Masterton/Hurley, Chemistry: Principles and Reactions, 8th Edition. © 2016 Cengage. All Rights Reserved. May not
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• Spin quantum number (ms) specifies the value
for the spin and is either +1/2 or -1/2.
No more than two electrons can occupy any
one orbital. In order for two electrons to
occupy the same orbital, they must have
opposite spins.
• Pauli’s exclusion principle, no two electrons in
an atom can have the same set of four
quantum numbers. This means no atomic
orbital can contain more than two electrons,
and if the orbital does contain two electrons,
they must be of opposite spin.
 The Pauli Exclusion Principle and Electron
Configurations

• Pauli Exclusion Principle - no two electrons in an

atom may have the same set of four quantum
numbers.

– Two electrons can have the same values of n, l, and ml,

but different values of ms.

– Two electrons maximum per orbital.

– Two electrons occupying the same orbital are spin

paired.
If an electron is paired up in a
box, one arrow must be
written up and the second
must be down.
This is incorrect, electrons
must spin in opposite
directions:

This is correct, the electrons

have opposite spins:
 Hund’s Rule and the Aufbau Principle
• Aufbau principle - when filling orbitals, start with the
lowest energy and proceed to the next highest
energy level.
• Hund’s rule - within a subshell, electrons occupy the
maximum number of orbitals possible.
• Electron configurations are sometimes depicted
using boxes to represent orbitals. This depiction
shows paired and unpaired electrons explicitly.
 Orbital Confugurations

• This sublevel configuration can be broken

down into orbitals (boxes).

Rules:

• Aufbau Principle - electrons fill orbitals

starting at the lowest available energy
state before filling higher states (1s before
2s).

• Pauli Exclusion Principle - an orbital can

hold 0, 1, or 2 electrons only, and if there
are two electrons in the orbital, they must
have opposite (paired) spins.
 Hund’s Rule and the Aufbau Principle

• A simplified depiction uses superscripts to indicate the

number of electrons in an orbital set.

– 1s2 2s2 2p2 is the electronic configuration for carbon.

• Noble gas electronic configurations are used as a

shorthand for writing electronic configurations.

– Relates electronic structure to chemical bonding.

– Electrons in outermost occupied orbitals give rise to chemical
reactivity of an element.
– [He] 2s2 2p2 is the shorthand for carbon
• On the left we have a diagram to show how
the orbitals of a subshell are occupied by
electrons. On the right there is a diagram for
the filling order of electrons in a subshell.
 The Periodic Table and Electron Configurations

• The periodic table and the electronic configurations

predicted by quantum mechanics are related.

– The periodic table is broken into s, p, d, and f blocks.

– Elements in each block have the same subshell for the

highest electron.

– Structure of periodic table can be used to predict electronic

configurations.
 The Periodic Table and Electron Configurations

• The shape of the periodic table can be broken down into blocks
according to the type of orbital occupied by the highest energy
electron in the ground state.
• We find the element of interest in the periodic table and write its
core electrons using the shorthand notation with the previous rare
gas element. Then we determine the valence electrons by noting
where the element sits within its own period in the table.
 Complete Electron Configuration
A. What is the electron configuration for Ne?
B. Ne: 1s22s22p6
C. What is the electron configuration for Mg?
D. Mg: 1s22s22p63s2
E. What do both electron configurations have
in common?
F. [Ne] =1s22s22p6
 Noble Gas Configuration
(Abbreviated Configuration)
A. Using neon’s configuration and then adding
magnesium’s extra electrons we can get the
noble gas configuration.
B. Ne: 1s22s22p6
C. Mg: 1s22s22p63s2
D. Noble gas configuration Mg: [Ne]3s2
E. Only use noble gases in the brackets.
 Question Time
• Try other s-block elements. Write the noble
gas configuration of the following elements
• Cs
• Ca [Xe]6s 1
1

• Ba [Ar]4s2 23
[Xe]6s 2 4
5
6
7
 Question Time
• Try other p-block elements. Write the noble
gas configuration of the following elements
• N
• S [He]2s22p3 1
• Cl [Ne]3s23p4 23
[Ne]3s 3p 5
2 54
6
7
 Example Problem
• What is the electron configuration for the
sulfur atom?
 Example Problem
• Rewrite the electron configuration for sulfur
using the shorthand notation.
 Periodic Trends in Atomic Properties

• Using the understanding of orbitals and

atomic structure, it is possible to explain some
periodic properties.

– Atomic size

– Ionization energy

– Electron affinity
 Atomic Size
• The shell in which the valence electrons are
found affects atomic size.
– The size of the valence orbitals increases with n, so
size must increase from top to bottom for a group.
• The strength of the interaction between the
nucleus and the valence electrons affects atomic
size.
• The effective nuclear charge increases from left to right
across a period, so the interaction between the electrons
and the nucleus increases in strength.
• As interaction strength increases, valence electrons are
drawn closer to the nucleus, decreasing atomic size.
The size of an atom is determined largely by
its valence electrons.
Valence electrons occupy the outermost
orbitals.

Atomic size increases from top to bottom for

a group.
Atomic size decreases from left to right for a
period.
 Example Problem
• Using only the periodic table, rank the
following elements in order of increasing size:
Fe, K, Rb, S, and Se.
 Formation of Ions

• Sizes of ions compared to corresponding neutral atoms.

 Ionization Energy
• Ionization energy - the energy required to remove an
electron from a gaseous atom, forming a cation.
– Formation of X+ is the first ionization energy, X2+ would be the
second ionization energy, etc.

– Effective nuclear charge increases left to right across a period.

– The more strongly held an electron is, the higher the ionization
energy must be.
– As valence electrons move further from the nucleus, they
become easier to remove and the first ionization energy
becomes smaller.
 Ionization Energy

• Graph of the first ionization energy (in kJ/mol) vs.

atomic number for the first 38 elements.
 Ionization Energy
• From nitrogen to oxygen, there is a slight decrease in
ionization energy.
– Nitrogen has a half-filled p subshell.
– Oxygen has a pair of p electrons in one 2p orbital.
– Ionization of oxygen relieves electron-electron repulsion,
lowering its ionization energy.

• Ionization energies increase with successive ionizations for

a given element.
– Effective nuclear charge for valence electrons is larger for the ion
than the neutral atom.

• Filled subshells of electrons are difficult to break up, which

is why it is difficult to remove electrons from noble gases.
 Example Problem
• Using only the periodic table, rank the
following elements in order of increasing
ionization energy: Br, F, Ga, K, and Se.
 Electron Affinity
• Electron affinity - energy required to place an electron on a
gaseous atom, forming an anion.

– Electron affinities may have positive or negative values.

• Negative values - energy released
• Positive values - energy absorbed

• Electron affinities increase (numerical value becomes more

negative) from left to right for a period and bottom to top
for a group.

• The greater (more negative) the electron affinity, the more

stable the anion will be.
 Electron Affinity

• Graph of electron affinity (in kJ/mol) vs. atomic number for

the first 20 elements.