Electronic Orbitals

Electronic Orbitals
Topics

• Wave-Particle Duality Theory

• Quantum Numbers
• Electronic Configurations of Atoms
• The Periodic Table
• Electronic Configurations of Ions
• Special Electronic Configurations – Transition Metals & Ions

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 Electronic Orbitals
Wave-Particle Duality Theory
• Isaac Newton (in 17th century) theorised that light consists of
a beam of particles
• However, Thomas Young (1801) demonstrated that light, like
waves, undergoes diffraction (i.e. spreads out when
encountering a small obstruction or a small hole)
• The wave theory was accepted until the early 20 th century
until Albert Einstein theorised that light has both wave and
particle properties to explain the photoelectric effect

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 Electronic Orbitals
Wave-Particle Duality Theory – Photoelectric Effect

• The photoelectric effect is the ejection of electrons from the

surface of a metal or another material when light shines on it.
Electrons only receive enough energy to be ejected when the
frequency of the light exceeds a certain threshold value
characteristic of the particular metal

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 Electronic Orbitals
Wave-Particle Duality Theory – Photoelectric Effect
• Increasing the intensity of lower frequency light does not
cause any electrons to be ejected
• Increasing the intensity of light at the threshold frequency
causes more electrons of the same energy to be ejected
• Shining light at frequencies above the threshold frequency
causes higher energy electrons to be ejected
• This effect can be explained by a particulate theory of light: If
light consists of particles (called photons) then only those
photons with the right energy (and thus frequency) can cause
an electron of a particular energy to be ejected. Increasing the
intensity of light of the wrong frequency/energy would have
no effect

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 Electronic Orbitals
Wave-Particle Duality Theory
• Wave theory of light explains properties such as diffraction &
refraction
• Particle theory of light explains properties such as line spectra & the
photoelectric effect
• Max Planck’s equation E = h links the wave and particle properties
of light, where E is the energy of a light particle (photon) and  is
the frequency of the associated wave
• Louis de Broglie (in 1924) suggested that the wave-particle duality
theory could also be applied to particles of matter i.e. particles of
matter, such as electrons, also have wave properties

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 Electronic Orbitals
Wave-Particle Duality Theory
• Because the wave motion of particles
becomes more significant as the mass of an
object gets smaller and smaller, classical
mechanics laws such as Newton’s Laws of
Motion fall apart (i.e. do not work) to predict
the motion of subatomic particles such as
electrons.
• New quantum mechanical laws had to be
derived
• Erwin Schroedinger built on de Broglie’s
wave-particle duality theory and calculated
wave equations for electrons in an atom
• The solutions to these wave equations give
the probability density of the electron i.e.
the probability of finding the electron in a
certain region of space the atom. 7
 Electronic Orbitals
Atomic Orbitals

• The volume of space in which there is a 95% chance of finding

the electron is called the atomic orbital
• (There is a 5% probability that the electron will be outside this
volume of space at any instant)
• In this model, the electron is not described as revolving in an
orbit. Instead, it is said to occupy a three-dimensional space
around the nucleus – the atomic orbital. The nucleus is
described as being surrounded by a three-dimensional “cloud
of charge” or “electron cloud”

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 Electronic Orbitals
Quantum Numbers

• Bohr’s one-dimensional electronic orbit model only needed

one quantum number n.

• Schroedinger’s three-dimensional model requires four

quantum numbers n, l , m, and s to describe the atomic
orbitals
• n = principal quantum number
l = angular quantum number
ml = magnetic quantum number
ms = spin quantum number

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 Electronic Orbitals
Quantum Numbers
• The principal quantum number n
– is the same as in the Bohr model
– describes the main energy level (or shell) of the electron
• The angular quantum number l
– Each principal electronic energy level (or shell) contains a number of
sublevels (or subshells) with different shapes s,p,d,f or g etc.
– The angular quantum number l describes the number of sublevels or
subshells of n and the shape of the orbitals
• The magnetic quantum number ml
– Each subshell contains different numbers of orbitals.
– The magnetic quantum number m l gives the maximum number of orbitals
within a subshell
• The spin quantum number ms
– gives the clockwise or anticlockwise orientation of the electron in the
orbital.
– It has values of +½ or -½
–  Each orbital can hold a maximum of two electrons
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 Electronic Orbitals
Number of Subshells
• Below are the subshells that occur for the first four energy levels:
Angular
Principal Number of
quantum Subshells
quantum shell subshells
number
n=1 l=0 s 1
l=0 s
n=2 2
l=1 p
l=0 s
n=3 l=1 p 3
l=2 d
l=0 s
l=1 p
n=4 4
l=2 d
l=3 f

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 Electronic Orbitals
Subshell Notation

• To denote a subshell within a particular shell, we write the n

quantum number of the shell, followed by the letter
designation for the subshell. E.g.

Third quantum shell 3s s subshell

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 Electronic Orbitals
Number of Orbitals
• Below are the orbitals that occur for the different subshells:

Number of
Angular momentum Values of ml
orbitals
quantum number ml = -l to +l
2l + 1
l = 0 (s subshell) 0 1
l = 1 (p subshell) -1,0,+1 3
l = 2 (d subshell) -2,-1,0,+1,+2 5
-3,-2,-
l = 3 (f subshell) 7
1,0,+1,+2,+3

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 Electronic Orbitals
Orbital Numbers and Shapes

• Every s subshell contains one spherical s orbital

• Every p subshell is split into three degenerate (equal in
energy) dumbbell-shaped p orbitals
• The p orbitals are at right angles to each other along x, y, and
z three-dimensional axes.
• Similarly, every d subshell is split into five degenerate d
orbitals. [You are not required to memorise the shapes of the
d orbitals for this course]

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 Electronic Orbitals
Orbital Numbers and Shapes

p orbitals all together

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 Electronic Orbitals
Orbital Sizes

• 2s orbitals are larger than 1s orbitals

• 3p orbitals are larger than 2p orbitals
Etc.

1s orbital 2s orbital

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Electronic Orbitals
Orbital Sizes

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 Electronic Orbitals
Number of Electrons
• Recall: Each orbital can only contain a maximum of 2 electrons
• So, for each type of subshell, the maximum number of
electrons possible is:

Subshell # Orbitals Max # Electrons

s 1 2
p 3 6
d 5 10
f 7 14

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 Electronic Orbitals
Subshells, Orbitals and Electrons
for the First 3 Quantum Levels

Max # electrons Total #

in electrons
Principal quantum
subshell in principal
shell
quantum
s p d shell
n=1 2 - - 2
n=2 2 6 - 8
n=3 2 6 10 18

•Recall: Each orbital can only contain a maximum of 2 electrons

•s subshell contains 1 orbital
•p subshell contains 3 orbitals
•d subshell contains 5 orbitals 19
 Electronic Orbitals
To put it simply…

• So, in the currently used quantum-mechanical model of the

atom, the electrons are still described as occupying several
energy levels n=1, n=2, n=3 etc.
• However, each energy level is pictured as containing one or
more sublevels within it, denoted by the letters s, p, d, f etc.
• Within these sublevels are regions called orbitals, s, px, py, pz,
etc.
• No matter what it’s type or energy level is, each orbital can
only hold a maximum of two electrons

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 Electronic Orbitals
Electronic Configuration of Atoms
• The arrangement of the electrons of an atom in its shells and
subshells is termed the electronic configuration of the atom
• Knowing this arrangement assists with understanding various
chemical and physical properties of atoms, elements, and
molecules
• To determine the electronic configuration of an atom, the
relative energies of its subshells and orbitals need to be
known

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 Electronic Orbitals
Subshell Notation

• To denote a subshell within a particular shell, we write the n

quantum number of the shell, followed by the letter
designation for the subshell. E.g.

Third quantum shell 3s s subshell

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 Electronic Orbitals
Electronic Configuration of Atoms
• Within a particular energy level or shell, the energies of subshells
increase in the order: s < p < d < f
• As the distance from the nucleus increases, shells get closer
together and there is some overlap among the subshells
• *Note, for example, that when empty, the 4s subshell is slightly
lower in energy than the 3d subshell
• Thus, for the different shells and subshells, and orbitals, the
following energy arrangement occurs:

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 Electronic Orbitals
Electronic Configuration of Atoms
• The following Aufbau diagram can be used to determine the
order of energies of the different subshells:

6s
5s 5p
4s 4p 4d
3s 3p 3d
2s 2p
1s
• So, 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s etc.
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 Electronic Orbitals
Electronic Configuration of Atoms

• The arrangement of electrons in orbitals can be worked out as

follows:
1. In a normal atom in the ground state, electrons are normally
arranged so that the energy is at a minimum. Electrons are
added to an atom one at a time beginning with the orbital of
lowest energy (Aufbau principle)
2. No more than two electrons can occupy an orbital (Pauli
Exclusion Principle)
3. Electrons fill degenerate orbitals one at a time with parallel
spin before a second electron is added with opposite spin
(Hund’s rule)

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 Electronic Orbitals
Electronic Configuration of Atoms

• The electronic configuration is normally written with the

principal quantum number (1, 2, 3,etc.) followed by the
symbol for the subshell (s, p, d, f, etc.), and a superscript that
shows the number of electrons in the orbital. E.g.

first quantum shell 1s2 2 electrons in orbital

s subshell

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 Electronic Orbitals
Electronic Configuration of Atoms - Examples
• H 1s1

• He 1s2

• Li 1s22s1

• C 1s22s22p2 or [He] 2s22p2

(short form based on last noble gas)

• O 1s22s22p4 or [He] 2s22p4

(short form based on last noble gas)

• P 1s22s22p63s23p3 or [Ne] 3s23p3

(short form based on last noble gas)
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 Electronic Orbitals
Electronic Configuration of Hydrogen – In Detail
• H
• atomic #: 1
• # e- : 1
• electronic configuration:

1s1

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
Electronic Configuration of Helium – In Detail
• He
• atomic #: 2
• # e- : 2
• electronic configuration:

1s2

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
Electronic Configuration of Lithium – In Detail
• Li
• atomic #: 3
• # e- : 3
• electronic configuration:

1s2 2s1

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
Electronic Configuration of Carbon – In Detail
• C
• atomic #: 6
• # e- : 6
• electronic configuration:

1s22s22p2
Or [He]2s22p2

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
Electronic Configuration of Oxygen – In Detail
• O
• atomic #: 8
• # e- : 8
• electronic configuration:

1s22s22p4
Or [He]2s22p4

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
Electronic Configuration of Phosphorous – In Detail
• P
• atomic #: 15
• # e- : 15
• electronic configuration:

1s22s22p63s23p3
Or [Ne]3s23p3

• Recall:
– Electrons are added to an atom one at a time beginning with the orbital
of lowest energy (Aufbau principle)
– No more than two electrons can occupy an orbital (Pauli Exclusion
Principle)
– There are three p orbitals that can each hold a maximum of 2 electrons
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 Electronic Orbitals
“Electrons in Boxes” Diagrams

• “Electrons in boxes” diagrams can be used to represent the

arrangements of the electrons in the orbitals

one orbital

electron with clockwise spin electron with anticlockwise spin

(ms = +1/2) (ms = -1/2)

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 Electronic Orbitals
Electronic Configuration of Atoms –
“Electrons in Boxes” Examples
• H 1s1
1s
• He 1s2
1s
• Li 1s22s1
1s 2s
• C 1s22s22p2
Or [He]
or [He] 2s22p2
1s 2s 2p 2s 2p
• O 1s22s22p4
or [He] 2s22p4
1s 2s 2p
• P 1s22s22p63s23p3
or [Ne] 3s23p3
1s 2s 2p 3s 3p 35
 Electronic Orbitals
Electronic Configuration of Carbon –
“Electrons in Boxes” Diagram
• C
• atomic #: 6
• # e- : 6
• electronic configuration: 1s22s22p2

C
1s 2s 2p
• Recall: Electrons fill degenerate orbitals one at a time with parallel
spin before a second electron is added with opposite spin (Hund’s
rule). Electron pairing occurs after there is at least one electron in
each of the degenerate orbitals.
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 Electronic Orbitals
Electronic Configuration of Oxygen –
“Electrons in Boxes” Diagram
• O
• atomic #: 8
• # e- : 8
• electronic configuration: 1s22s22p4

O
1s 2s 2p
• Recall: Electrons fill degenerate orbitals one at a time with parallel
spin before a second electron is added with opposite spin (Hund’s
rule). Electron pairing occurs after there is at least one electron in
each of the degenerate orbitals.
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 Electronic Orbitals
Electronic Configuration of Atoms –
“Electrons in Boxes” Examples
• H 1s1
1s
• He 1s2
1s
• Li 1s22s1
1s 2s
• C 1s22s22p2
Or [He]
or [He] 2s22p2
1s 2s 2p 2s 2p
• O 1s22s22p4
or [He] 2s22p4
1s 2s 2p
• P 1s22s22p63s23p3
or [Ne] 3s23p3
1s 2s 2p 3s 3p 38
 Electronic Orbitals
Energy Level Diagrams

• Energy level diagrams can also be used to show electronic

configurations
Bohr Energy Level Diagram

n=3
Energy
n=2

n=1 39
 Electronic Orbitals
Energy Level Diagrams
Modern Energy Level Diagram including subshells and orbitals

3p n=3
Energy 3s

n=2 shell (2)

2p
2s
subshell (2p)
can contain 2
electrons max orbital (e.g. 2pz)
with opposite
n=1
spins 1s

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 Electronic Orbitals
Energy Level Diagrams
Modern Energy Level Diagram including subshells and orbitals

3px 3py 3pz n=3

Energy 3s 3p

n=2 shell (2)

2px 2py 2pz
2s 2p subshell (2p)
an orbital can
contain 2 orbital (2pz)
electrons max
n=1
with opposite 1s
spins
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 Electronic Orbitals
Electronic Configuration of Oxygen –
Energy Level Diagram
Energy Level Diagram for an Oxygen Atom
(electronic configuration: 1s22s22p4)

3p n=3
Energy 3s

n=2
2p
2s

n=1
1s
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 Electronic Orbitals
The Periodic Table
• The periodic table is a listing in chart form of the known
elements.
• It has undergone many variations and attempts to list the
elements based on observed periodic or repeating properties.
• Currently it is based in order of increasing atomic numbers
• Horizontal rows of elements are called periods numbered 1, 2,
3 etc. corresponding to the principal quantum number
• Vertical rows of elements are called groups numbered 1-18
(IUPAC) or I-VIII (older form)
• Elements in a group have similar electronic configurations and
properties
• E.g. outer electrons: Group I: ns1, Group II: ns2, Group IV: ns2np2
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Electronic Orbitals
The Periodic Table
VIIIA

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 Electronic Orbitals
The Periodic Table
• The periodic table can be divided into “blocks” based on the
subshell being filled by the outer electrons. This allows us to
quickly determine the electronic configuration of an element
by simple inspection of it’s row and group.
s block p block

d block

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Electronic Orbitals
•He 1s2
The Periodic Table •C 1s22s22p2
•O 1s22s22p4
•P 1s22s22p63s23p3
VIIIA
or [Ne] 3s23p3

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 Electronic Orbitals
Electronic Configuration of Ions

• To write the electronic configuration of ions, use the number

of electrons remaining in the atom after the ion has been
formed
• So, for negatively charged ions (anions), there will be more
electrons than for the neutral atom
• Whereas for positively charged ions (cations), there will be
fewer electrons than for the neutral atom

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 Electronic Orbitals
Electronic Configuration of Ions - Examples
Recall uncharged O atom:
• O2-
• atomic #: 8
• # e- : 10
• electronic configuration: 1s22s22p6

O2–
1s 2s 2p

• This electronic configuration is equivalent to that of the noble

gas Ne

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 Electronic Orbitals
Electronic Configuration of Ions - Examples

• Ca2+
• atomic #: 20
• # e- : 18
• electronic configuration: 1s22s22p63s23p6

Ca2+
1s 2s 2p 3s 3p
• This electronic configuration is equivalent to that of the noble
gas Ar
Comparing with neutral Ca atom:

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 Electronic Orbitals
Special Electronic Configurations – Transition Elements

• As the energy levels get further from the nucleus the distance
between them decreases rapidly
• At higher energy levels there is some overlap of the subshells
associated with different energy levels
• E.g. the empty 4s orbital is actually slightly lower in energy
than the empty 3d orbitals and is filled first for the 1st row
transition elements

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 Electronic Orbitals
Special Electronic Configurations – Transition Elements

Sc (atomic #: 21)
1s22s22p63s23p64s23d1 [Ar]
or [Ar]4s23d1 4s 3d

Ti (atomic #: 22)
[Ar]4s23d2 [Ar]
4s 3d

V (atomic #: 23)
[Ar]4s23d3 [Ar]
4s 3d
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 Electronic Orbitals
Special Electronic Configurations – Transition Elements

• An anomaly occurs for the element with atomic number 24.

• Instead of having a full 4s orbital, one electron is moved to a
3d orbital to give a very stable half-filled d subshell:
Cr (atomic #: 24)
[Ar]4s13d5 [Ar]
4s 3d

• Filling of the 3d orbitals then continues as normal for the next

4 elements:
Mn (atomic #: 25)
[Ar]
[Ar]4s23d5
4s 3d
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 Electronic Orbitals
Special Electronic Configurations – Transition Elements

Fe (atomic #: 26)
[Ar]
[Ar]4s23d6
4s 3d

Co (atomic #: 27)
[Ar]
[Ar]4s23d7
4s 3d

Ni (atomic #: 28) [Ar]

[Ar]4s23d8 4s 3d 53
 Electronic Orbitals
Special Electronic Configurations – Transition Elements

• Another anomaly occurs for atomic number 29

• Again, instead of having a full 4s orbital, one electron is moved
to a 3d orbital to give a very stable completely filled d subshell:

Cu (atomic #: 29)
[Ar]4s13d10 [Ar]
4s 3d

• Finally, Zn (atomic # 30) has both the 4s and 3d orbitals

completely filled:
Zn (atomic #: 30) [Ar]
[Ar]4s23d10
4s 3d
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 Electronic Orbitals
Special Electronic Configurations – Transition Elements
Sc Co

[Ar] [Ar]
4s 3d Ti
4s 3d
Fe
[Ar] [Ar]
4s 3d V 4s 3d
Ni
[Ar] [Ar]
4s 3d Cr 4s 3d Cu

[Ar] [Ar]
4s 3d Mn 4s 3d
Zn

[Ar] [Ar]
4s 3d 4s 3d 55
 Electronic Orbitals
Special Electronic Configurations – Transition Metal Ions
• Although the unfilled empty 4s orbital is lower in energy than the
unfilled 3d orbitals, once electrons are present, the 4s orbtial
become slightly higher in energy than the 3d orbitals. So, electron
loss to form ions happens from the 4s orbital first. i.e. the 4s
orbitals are filled first but are emptied first. Thus all the first row
transition metals form stable 2+ ions.
E.g. 2+ 2 0
Ti (atomic #: 22) [Ar] 3d 4s

[Ar]
3d 4s
Cr2+ (atomic #: 24) [Ar] 3d44s0

[Ar]
3d 4s 56