Molecular Orbitals

VSEPR & MO Theory

Overview
▪ Geometry of Molecules
▪ Dipole moments
▪ Valance Bond Theory
▪ Hybridization
▪ Molecular Orbital Theory
▪ Delocalisation
Problem
How many unpaired electrons with C
Lewis: 4 Hund’s rule: 2

2p

C 2s

1s
Reconcile This
▪ Bonds are the pairing of unpaired electrons
▪ Carbon almost always forms 4 Bonds CH 4 for example is methane
▪ Lewis seems to show 4 bonds but this is not a complete picture
▪ Atomic orbitals with hunds rule seems to suggest 2
▪ A more complete picture is that atomic orbitals are not the same as
molecular orbitals and that forming a bond changes the electron orbitals
▪ In short Molecular Orbitals ≠ Atomic Orbitals

Today we look at theories that address molecular orbitals

Geometry
▪ We will start with a discussion of
geometry
▪ Geometry is the 3D arrangement of the
atoms in the molecule
▪ It is responsible for a host of physical
properties such as density and melting
points
Simple Geometry Prediction
▪ A simple method to work out the
geometry is to use the number of
(paired or singular) electron
120o 120o
around the atom
▪ Lewis structure of molecules is a
good start for working this out
120o
▪ From there we arrange them so
that they have maximum
separation
Recap Bonding Pair
▪ When you make a bond you make a
pair of electrons
H
HC H
▪ This bonding pair is responsible for
keeping them together
Bonds Repel
▪ The electrons in these bonds can
be thought of as repelling one-
H
HC H
another
▪ This means that bonds will be as-
far apart as possible to minimise
the repulsion
VESPR: Valence Electron Shell
Pair Repulsion
▪ This is the basis for VESPR
▪ This theory can account for the 3d
geometry of molecules around a
central atom
Procedure
▪ Start with the molecules Lewis structure
▪ If there is multiple resonance structure just pick any of them

▪ Repel: Move the bonds/lone pairs away from each other to maximise the
space
▪ Treat double/triple bonds the same as single for the arrangement
Simple Cases (No Lone Pairs)
▪ Lets start with a basic 𝐴𝐵𝑥 ▪ X=1 Diatomic, just a straight line
structure
▪ A is the central atom
▪ B is the surrounding atoms
▪ x is the number of such
surrounding atoms
▪ There are no lone pairs (on central
atom) yet
AB 2 : BeCl 2
▪ Two molecules surrounding the
central atom also yields a straight
line
▪ The electron pairs in the bond
repel to the maximum extend and
are on other sides of the atom 180o
AB 3 : BF 3
▪ Three atoms results in a triangular
like shape
▪ This is called trigonal planar 120o 120o

120o
AB 4 : CH 4
▪ The first shape with three
dimensions (non planar) is when
there are 4 atoms
109.5o 109.5o
▪ This shape is called a tetrahedron
all the atoms are 109.5 o apart in all
directions
109.5o 109.5o
AB 5 : PCl 5
▪ To get these latter structures
requires the extended octet rule
(more than 8) so third row and
90o
onwards in the periodic table
▪ This one is called trigonal bi- 120o
pyramidal
▪ It is like 2 triangle based pyramids
mirroring each other in the ground
plane
▪ Those in the plane are EQUITORIAL
▪ Those above and below are AXIAL
AB 6 : SF 6
▪ Finally we have octahedral (a lot of
transition elements are like this)
90o
▪ This is also called square based
bipyramidal
90o 90o
▪ All bonds are at 90 to each other
(except those directly across)
Lone Pair Effects
▪ When lone pairs surrounding the

Medium

Weakest Repulsion
Strongest Repulsion
central atom they act like another Lone Lone Bonding
bond that repels near by atoms Pair with Pair with Pair with
▪ EXCEPT their repulsion is stronger Lone Bonding Bonding
▪ They are a full pair electrons not a Pair Pair Pair
shared pair
▪ They are larger (since they are not
shared) and take up more space
nearer the atom repelling other
bonds away
 E for lone pair of Electrons

AB 2 E: SO 2
As a result
of the
▪ Lewis Structure for SO2 is: additional
Lone Pair
repulsions

O S O
>120o >120o the angles
are not all
120o

<120o
▪ Which might make you think linear
▪ But that Lone pair on the S is more
repulsive
 E for lone pair of Electrons

AB 3 E: NH 3
As a result
of the
▪ NH3 also have a lone pair making it additional
tetrahedral like Lone Pair
repulsions

H N H
>109.5o the angles
are not all
109.5o

<109.5o

H
 E for lone pair of Electrons

AB 2 E 2 : OH 2
As a result
of the
▪ Water has two lone pairs making it additional
a bent molecules with a much Lone Pair
repulsions
smaller angle than 120 o
the angles
are not all

H O
109.5o

<109.5o

H
Tetrahedral Angles
▪ Long pairs have a greater repulsive effect and push the other bonds closer
together

0 Lone Pairs 1 Lone Pair 2 Lone Pairs

 E for lone pair of Electrons

AB 4 E: SF 4
▪ Now observing the molecules in
the extended octet rule so based of
the bipyramidal shapes
▪ There are two possible
arrangements for SF4
▪ One with the lone pair AXIAL
▪ One with the lone pair EQUITORIAL
 E for lone pair of Electrons

AB 4 E: SF 4
▪ The equatorial one is more stable
since it gives maximum space for
the lone pair
▪ Because of the greater repulsive
nature of the lone pair it is called
the distorted tetrahedron or the
seesaw
 E for lone pair of Electrons

AB 3 E 2 : ClF 3
▪ Two lone pairs make it T shaped
(but distorted of course by the lone
pairs)
 E for lone pair of Electrons

AB 2 E 3 : I 3 -

▪ Three lone pairs bring it back to

linear with all of the lone pairs on
the equatorial positions
 E for lone pair of Electrons

AB 5 E: BrF 5
▪ The octahedral ones are quite
symmetric with all bonds originally
at 90 o so relatively easy to imagine
how a long pair will affect them
▪ This is square based pyramid
 E for lone pair of Electrons

AB 5 E 2 : XeF 4
▪ This last shape is common with the
latter transition metals
▪ It is square planar
▪ Both lone pairs are on opposite
ends
More than 1 Central Atom
▪ When there is more than 1 central
atom it can be hard to apply
VESPR
▪ But for simple structures we can
apply the theory to each central
atom one at a time Bent
Tetrahedral Tetrahedral
109.5o 109.5o

109.5o 109.5o <109.5o

VESPR Guidelines
▪ Work out the lewis structure (helps
with lone pairs)
Number of Pairs Shape
▪ Count the electron pairs around 1 Linear
the central atom
2 Linear
▪ Treat double and triple as single
3 Trigonal
▪ Predict overall geometry based on 4 Tetrahedral
the number of pairs 5 Trigonal bipyramidal
▪ Predict qualitatively the effect the 6 Octahedral
lone pairs will have
It’s a Model
▪ Please do be aware that we use
this as a model
▪ There are concerns about electrons
not actually repelling in this fashion

▪ It is quite effective at qualitative

predictions of the structure for
most simple molecules
What about Ethene?
▪ Can you guess this molecules
shape?
▪ Two sets of trigonal with all angles
at 120
▪ Additionally the double bond
cannot rotate very much and it is
planar across the bond because of
the orbital arrangement that we
will see later
 Dipole
Moment
Unequal sharing again
HF a Polar Bond
▪ Earlier we learnt that HF is a polar
covalent bond
▪ There is a shift in electron density
towards the F
▪ We can represent this as a crossed
arrow
HF a Polar Bond
▪ Or as a partial charge with a
+ −
𝛿 𝑜𝑟 𝛿
▪ Where 𝛿 + represents a partial
positive change and 𝛿 − a negative
Experimentally
▪ This partial charge can be detected ▪ Since the quantity for a single
experimentally as a dipole moment molecule is so small it is usually
𝜇 =𝑄×𝑟 expressed in Debye units
▪ To maintain neutrality the charges 1 𝐷 = 3.336 × 10 −30 𝐶 𝑚
are oppositely charged with the
same magnitude
▪ Q however is unsinged so that 𝜇 is
always positive
Two Atoms
▪ With just two atoms they have
dipole moments when the atoms
are different
▪ HF being our current example
For Three Atoms
▪ For more than 2 atoms though you
must consider its geometry
▪ CO2 for example can either be
▪ Without a dipole moment if linear
▪ With a dipole moment if bent

Experimentally
CO2 has no
dipole moment
so its this one
More Atoms (and a Lone Pair)
▪ For more atoms we need to apply
the same concepts
▪ Write the direction of the individual
dipoles and sum that up (as a
vector quantity)
▪ This can mean that certain dipoles
cancel
▪ For example N-F is a more polar
bond than N-H but its net dipole
moment is smaller
Dipole Moment Uses
▪ We can use dipole moments to
deduce a structure
▪ Consider di-chloro-ethylene
▪ This can have the Cl atoms either
on the same side or on opposite
side
▪ Recall that double bonds don’t
rotate

▪ This means we can use the dipole

moment to work out which
structure is true
Valence Bond Theory
Why Bond?
▪ Lewis theory and VESPR gives us a ▪ Lewis theory treats all bonds in the
good idea of geometry but it same way
doesn’t explain why bonds form
▪ H-H and F-F in lewis and VESPR
▪ What is the energetic gain from are the same
making a bond? ▪ But their strengths are vastly
different
▪ Why is a bond more stable (lower
in energy) ▪ To address this we must turn to
quantum mechanics
Two Theories
Valence Bond Theory MO Theory
▪ Assumes electrons occupy ▪ Assumes electron occupy
combined atomic orbitals from a combined atomic orbitals from
atom multiple atoms
▪ Simpler ▪ More complex
▪ Retains the idea of atoms within ▪ Treats molecules as the complete
molecules whole

Neither theory is perfect but they get close

Orbital Overlap
▪ Where as lewis is the sharing of
two electrons
▪ Valance bond theory describes
bonds as overlapping orbitals
At a Distance
▪ When two atoms are far apart we
say there is no interaction
▪ ZERO energy from the bond
Closer
▪ Closer the electrons will be
attracted to the other nucleus
▪ They will also be repelled by the
other electrons
▪ This is a net decrease in potential
energy (more negative)
▪ This continues until it reaches a
minimum (the bond length)
Too Close
▪ Even closer and the electrons and
nuclei repel
▪ There is a sharp increase in
potential energy (positive)
resulting in unstable situation
Energy
▪ Wait negative?
▪ Yes negative we consider unbound
to be zero energy
▪ As we move closer together the
molecules energy decreases to a
more stable state
▪ Since the molecule energy
decreases that energy is released
into the surrounding as exothermic
Orbital Changes
▪ As the orbitals get closer they
overlap
▪ The add together constructively
making a region of increased
electron density between them
▪ Since the orbitals are different then
adding different atoms (H-H and F-
F) should account for energetic
differences
Hybridisation
The beginning of MO
VBT
▪ Valance bond theory treats bond as the overlap of atomic orbitals with
unpaired electrons
▪ This is much like Lewis structure but focusing on the AO rather than the
electrons
Carbon has … Unpaired e -

▪ According to AO theory:
Carbon only has how many
unpaired electrons?
Carbon has 2 Unpaired e -

▪ In atomic orbitals (that VBT uses)

carbon has 2 unpaired electrons
▪ How can carbon make 4 bonds?
VBT Solution: Promotion
▪ To solve this VBT theory says we
can:
▪ Promote (excites) the electrons in
2s into 2p
▪ By doing this we also have 4 Energy
unpaired electrons

▪ This requires energy

▪ Which we get more than get back by
making 2 extra bond
Geometry?
▪ VBT treats bonds as the overlap of
orbitals
▪ But this leaves issues with their 3d
structure look at a C atoms atomic
orbitals
▪ If we overlap with those p orbitals
we would need to bond at 90 o just
like the orbitals
VBT Solution: Hybridisation
▪ To account for this VBT creates
new molecular orbitals by
combining atomic orbitals (from
the same atom)
▪ By mixing orbitals the shape
changes
Hybridisation
𝒔𝒑 𝟑 orbitals
▪ sp3 are the mixing of all the s and p
orbitals
▪ They look like p orbitals with one
side much larger
▪ They also point at the tetrahedral
direction
𝒔𝒑 𝟑 orbitals Lone Pairs too
▪ We mix orbitals when the VESPR
tells us to (another technique can
also tell when to mix)
▪ Lone pairs can be mixed too such
as in NH3
𝒔𝒑 hybridisation
▪ Sp hybridisation yield a linear
geometry
▪ Such as with BeCl2
▪ Again there is an initial promotion
to move the 2s into the 2p and Energy
make 2 unpaired electrons
𝒔𝒑 hybridisation
▪ Hybridising an s and p yields 2 ▪ The number of orbitals created
orbitals pointing away from each equals the number started with
other
𝑠𝑝 2 hybridisation
▪ sp2 hybridisation yields the
trigonal shape of VESPR
Extended Octet
▪ Going further then sp3 requires the
extended octet and the use of d
orbitals
▪ These are only available for third
row elements where there are d Energy
orbitals available
▪ This lets us form more bonds
▪ But the procedure is the same
promote electrons and combine
orbitals
All the Hybridisations
𝑠𝑝 𝑠𝑝2

𝑠𝑝3

𝑠𝑝3 𝑑 𝑠𝑝3 𝑑2
Multiple Bonds &
Hybridisation
Double Bonds
▪ Consider Ethylene
▪ It is sp2 hybridised so trigonal
orientation
Unhybridized p Orbital
▪ This also means that 2p z is
unhybridised but still has a free
electron
p z overlap
▪ This remaining 2pz can interact
with the 2pz on the other C
▪ These two orbitals do not directly
point at each other
▪ But instead lie next to each other
▪ It is called a 𝜋 (pi) bond
Two Kinds of Bonds
𝜎 bonds 𝜋 bonds

▪ Usual bonds between atom ▪ Bonds out of the bonding plane

▪ Stronger ▪ Weaker
▪ Made from hybridized orbitals ▪ Made from p orbitals
Triple Bonds
▪ Triple bonds are made from 2𝜋
bonds
▪ This is when 2 p orbitals are free
to interact such as when there only
is sp hybridisation
VBT: Recap
▪ Is a theoretical MODEL to account ▪ Electrons are said to occupy the
for bonding orbitals of individual atom
▪ Hybridisation is the mixing of atom ▪ This last one is an issue
orbitals to create new orbitals ▪ A true description of electron
movement should account for its free
▪ Number of new hybrid orbitals = movement across the bond (and the
those that were used to create it molecule)
▪ Hybridisation required energy input
(recovered from the bond)
Molecular Orbital Theory
Failure of VBT
▪ VBT cannot account for certain
features of molecules particularly
magnetic properties
▪ It still relies on Lewis structures
and paired electrons between
▪ According to Lewis structure if
molecules
diamagnetic (all electrons paired)
▪ For example O 2
▪ But experiments suggest it has 2
unpaired electrons
More Complete MO Theory
▪ A more complete theory is MO theory
▪ It can predict the true occupancy of electrons in orbitals
▪ Thus can predict accurately how many un-paired electrons it has (para-
magnetism stems from unpaired electrons)
Overlap Again but
with a Twist
▪ According to MO theory the overlap
of 2 atom orbitals
▪ Produces 2 molecular orbitals
▪ A bonding pair
▪ AND an anti-bonding pair
Constructive
▪ The bonding orbital pair occurs
when the two orbitals odd
constructively
▪ Much like two waves adding
together (recall that electrons are
also waves)
Destructive
▪ The destructive combination of
the two waves is also created
▪ In this case it is called an
antibonding orbital
▪ The destructive nature of the
two waves means that there IS
LESS ELECTRON DENSITY
LESS BONDING
MO Diagram
▪ We can draw this as an MO energy
level diagram
▪ The bonding orbital is more stable
than free atoms (lower in energy)
▪ The anti-bonding (notice the star in
𝜎 ⋆ denotes anti-) is less stable
 Constructive 𝜎2𝑝𝑥

P orbitals too
⋆
Destructive 𝜎2𝑝𝑥
▪ Constutive interference of p
orbitals makes 𝜋 orbitals
▪ While destructive makes 𝜋 ⋆
(pronounced as pi star)
⋆
Destructive 𝜋2𝑝𝑧

Constructive 𝜋2𝑝𝑧
Electron Orbital Configuration
▪ Number of MO is equal to the number of AO used to create it
▪ The more stable the bonding the less stable the antibonding
▪ Orbitals fill lowest energy first with 2 electrons per orbital
▪ When orbitals have the same energy use hunds rule to fill them
Bond Order
▪ The bond order of a molecule is
given by

𝑏𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟
1
= 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒 − − 𝑎𝑛𝑡𝑖𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒 −
2
▪ What would you expect these to
be?
1/2 1 1/2 0
Bond Order: Strength
▪ The higher the bond order the
stronger the bond
▪ This is a relative and qualitative
scale so double bond order does
not mean double strength
▪ In some rare cases even 0 bond
order can form a very very weak
bond
1/2 1 1/2 0
1s
▪ Lets’ start with the easy case same
atom diatomics
▪ Overlap of 1s orbitals are easy
▪ They are usually so low down in
energy that 2s and 2p cannot
effect them
Second Row
▪ From the second row we have 2s
orbitals
▪ For early elements like Li 2
▪ It fills up just like normal
P Orbitals
▪ P orbitals have an added
complication
▪ There are two kinds
▪ Those inline with the bond (sigma)
▪ Those outside of the bond (pi)
▪ The two out of plane pi orbitals (y
and z) have the same energy so are
shown as paired
Out of Order
▪ Also note the ordering
▪ The bonding pi orbitals are lower in
energy then the bonding sigma
▪ This is thought to occurs because
of the repulsion (or mixing) of the
2s orbital effecting the px more
than the py and pz (because the px
and 2s try to occupy the same
space)
Back in Order
▪ After N2 though (So O2 and F2) the
orbitals are not as effected by this
▪ So that the sigma p orbital is lower
in energy
▪ This is thought to happen because
of the greater effective charge
moving the 2s closer to the nucleus
and further away from the 2px
All The Molecules
▪ We can see that by filling up the molecule orbitals using the usual
rules gives the correct 2 unpaired electrons of O2
Delocalised MO
Recall Resonance
▪ Sometimes we cannot account for
all of the properties with one
structure using just normal bonds
▪ In lewis this was “resolved” with
resonance
▪ The idea that the molecule is
between 2 or more structures
MO Delocalised
▪ MO handles this problem in a
different way
▪ By using MOs to spread the
bonding electron over MULTIPLE
ATOMS
Benzene
▪ The sigma structure of benzene
from VESPR is sp2 hybridized so
trigonal shape
Benzene: Pi
▪ The interesting part is the pi
orbitals out of the plane
▪ A usual double bonding is when
these are next to each other
▪ BUT here they are ALL next to
each other ALL overlapping
Electrons Delocalise
▪ We say that the electrons are
delocalised (free to move about all
of those atoms)
▪ The electrons are evenly
distributed between partial pi
bonds
▪ This is the alternative the MO
offers instead of resonance
Fin
Workshop Time