MOLECULAR ORBITALS

MOLECULAR ORBITAL THEORY

 Molecular orbitals are obtained by combining the atomic orbitals on the

atoms in the molecule.
 Consider the H2 molecule, for example.
 One of these orbitals is called a bonding molecular orbital because
electrons in this orbital spend most of their time in the region directly
between the two nuclei.
 It is called a sigma (σ) molecular orbital because it looks like an s orbital
when viewed along the H-H bond.
 Electrons placed in the other orbital spend most of their time away from
the region between the two nuclei.
 This orbital is therefore an antibonding, or sigma star (σ*), molecular
orbital. 2
MOLECULAR ORBITAL THEORY
GUIDE TO FORMING MOLECULAR ORBITALS

 Determine how many valence electrons you have on each atom.

 This gives you the total number of electrons you will have to
distribute among the molecular orbitals you form. For example
consider B2, each B atom has an electron configuration of
[He]2s22p1 which has a total of 6 valence electrons.

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MOLECULAR ORBITAL THEORY
GUIDE TO FORMING MOLECULAR ORBITALS

 Draw a cartoon energy level diagram

with lines for the valence atomic
energy levels (orbitals) of each
atom. Put one atom's levels on the
left and one on the right. Include the
electrons.

 Leave space in the middle for your molecular energy levels

(orbitals). It can help to include cartoons of the atomic orbitals as 4

well. Shown for diboron immediately.

 MOLECULAR ORBITAL THEORY
GUIDE TO FORMING MOLECULAR ORBITALS

 Combine each pair of orbitals of

similar to create molecular
orbitals

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 Move the electrons from the atoms into the molecule to determine the
molecular electron configuration.
 MOLECULAR ORBITAL THEORY
PRINCIPLES OF MOLECULAR ORBITALS
Principle Details/Examples
Total number of molecular orbitals is equal The molecule H2 is composed of two H atoms. Both H atoms have a 1s
to the total number of atomic orbitals used orbital, so when bonded together, there are therefore two molecular orbitals.
to make them.
Bonding molecular orbitals are lower Electrons in bonding molecular orbitals help stabilize a system of atoms since
energy than the atomic orbitals from less energy is associated with bonded atoms as opposed to a system of
which they were formed. unbound atoms. Bonding orbitals are formed by in-phase combinations of
atomic orbitals and increase the electron density between the atoms (see
figure 2 below).
Antibonding molecular orbitals are Electrons in antibonding molecular orbitals cause a system to be destabilized
higher energy than the atomic orbitals since more energy is associated with bonded atoms than that of a system of
from which they were formed. unbound atoms. Antibonding orbitals are formed by out-of-phase
combinations of atomic orbitals and decrease the electron density between
atoms (see figure 2 below).
Following both the Pauli exclusion principle Electrons fill orbitals with the lowest energy first. No more than 2 electrons
and Hund's rule, electrons fill in orbitals of can occupy 1 molecular orbital at a time. Furthermore, all orbitals at an
increasing energy. energy level must be filled with one electron before they can be paired. (see
figure 3 below)
Molecular orbitals are best formed when When Li2 forms the two lowest energy orbitals are the pair of bonding and
composed of Atomic orbitals of antibonding orbitals formed from the two possible combinations of the 1s on
like energies. each atom. The 2s orbitals combine primarily with each other to form another
pair of bonding and antibonding orbitals at a higher energy.
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MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (1S)
 The hydrogen molecule: the simplest molecule

 To see how this works, we will consider the simplest possible molecule, H2.
This is the hydrogen molecule, which consists of two nuclei of charge , and a
two electrons shared between them

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MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S)

Molecular Orbitals of the Second Energy Level

 The 2s orbitals on one atom combine with the 2s orbitals on another to form
a 2s bonding and a 2s* antibonding molecular orbital, just like the 1s and 1s*
orbitals formed from the 1s atomic orbitals.
 The 2px atomic orbitals combine to form a x bonding molecular orbital and
a x* antibonding molecular orbital. The same thing happens when the 2py
orbitals interact, only in this case we get a y and a y* antibonding
molecular orbital.

 Because there is no difference between the energies of the 2px and

2py atomic orbitals, there is no difference between the energies of the x
and y or the x* and y* molecular orbitals. 8
MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S)

 The interaction of four valence atomic orbitals on one atom (2s, 2px, 2py
and 2pz) with a set of four atomic orbitals on another atom leads to the
formation of a total of eight molecular orbitals: 2s, 2s*, 2p, 2p*, x, y, x*, and y*.

 There is a significant difference between the energies of the 2s and 2p

orbitals on an atom. As a result, the 2s and *2s orbitals both lie at lower
energies than the 2p, 2p*, x, y, x*, and y* orbitals.

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 MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S)

HOMO stands for "Highest Occupied Molecular Orbital", and

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LUMO stands for "Lowest Unoccupied Molecular Orbital".
The LUMO is higher in energy than the HOMO
MOLECULAR ORBITAL
BOND ORDER AND STABILITY OF MOLECULES

 Bond Order indicates the strength of the bond with the greater the
bond order, the stronger the bond.

 If the bond order is zero, then no bonds are produced and the
molecule is not stable

 If the Bond Order is 1, then it is a single covalent bond. The higher the
Bond Order, the more stable the molecule is.

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MOLECULAR ORBITAL
BOND ORDER AND STABILITY OF MOLECULES
 Bond orders can be calculated from Lewis structures, which are the
heart of the valence-bond model. Oxygen, for example, has a bond order
of two.

 When there is more than one Lewis structure for a molecule, the bond
order is an average of these structures. The bond order in sulfur dioxide,
for example, is 1.5 the average of an S-O single bond in one Lewis
structure and an S=O double bond in the other.

 In molecular orbital theory, we calculate bond orders by assuming that

two electrons in a bonding molecular orbital contribute one net bond
and that two electrons in an antibonding molecular orbital cancel t he
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effect of one bond.
MOLECULAR ORBITAL
BOND ORDER AND STABILITY OF MOLECULES
 We can calculate the bond order in the O2 molecule by noting that there are
eight valence electrons in bonding molecular orbitals and four valence
electrons in antibonding molecular orbitals in the electron configuration of
this molecule. Thus, the bond order is two.
 Although the Lewis structure and molecular orbital models of oxygen yield the
same bond order, there is an important difference between these models.

 The electrons in the Lewis structure are all paired, but there are two unpaired
electrons in the molecular orbital description of the molecule.

 As a result, we can test the predictions of these theories by studying the effect
of a magnetic field on oxygen.
 An advantage of Molecular Orbital Theory when it comes to Bond Order is that it
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can more accurately describe partial bonds (for example in H2+, where the Bond
Order=1/2), than Lewis Structures.
MOLECULAR ORBITAL
MAGNETISM
 Atoms or molecules in which the electrons are paired are diamagnetic
repelled by both poles of a magnetic.

 Those that have one or more unpaired electrons are paramagnetic attracted
to a magnetic field.

 The molecular orbital model of O2 is therefore superior to the valence-bond

model, which cannot explain this property of oxygen.

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MOLECULAR ORBITAL
MAGNETISM
 None of the other bonding models can predict the presence of two unpaired
electrons in O2. Chemists had long wondered why, unlike most other
substances, liquid O2 is attracted into a magnetic field.

 Liquid oxygen poured in between two poles of a magnet actually remains

suspended between the poles of a magnet until the liquid boils away.

 The only way to explain this behavior was for O2 to have unpaired electrons,
making it paramagnetic, exactly as predicted by molecular orbital theory.

 This result was one of the earliest triumphs of molecular orbital theory over
the other bonding approaches we have discussed.
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MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S): O2

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MOLECULAR ORBITAL
LEARNING CHECK

Draw the molecular orbital diagram for the fluorine atom, determine the
bond order and magnetism.

Bond order = (B e- __ Anti-b e-)/2

= 8-6/2= 1

It is diamagnetic because of the paired electrons

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MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S AND 2PZ)

 It is possible for the 2s orbital on one atom to interact with the 2pz orbital
of the other atom. This interaction introduces an element of s-p mixing, or
hybridization, into the molecular orbital theory.

 The result is a slight change in the relative energies of the molecular

orbitals, to give the diagram shown in the figure below.

 Experiments have shown that O2 and F2 are best described by the model in
the figure above, but B2, C2, and N2 are best described by a model that
includes hybridization, as shown in the figure below.

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MOLECULAR ORBITAL
EXAMPLE – HOMONUCLEAR (2S AND 2PZ)

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MOLECULAR ORBITAL
LEARNING CHECK

Draw the molecular orbital diagrams of the Boron (B2), Carbon (C2) and
Nitrogen (N2) molecules. Determine the bond order to describe the type of
bond and magnetism.

How are these different from the molecular orbitals of oxygen and fluorine?

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MOLECULAR ORBITAL
SOLUTION: B2

Bond order = (B e- __ Anti-b e-)/2

= (4-2)/2= 1

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It is paramagnetic because of the unpaired electrons
MOLECULAR ORBITAL
SOLUTION: C2

Bond order = (B e- __ Anti-b e-)/2

= (6-2)/2= 2
double bond 22

It is diamagnetic because of the paired electrons

MOLECULAR ORBITAL
SOLUTION: N2

Bond order = (B e- __ Anti-b e-)/2

= (3-2)/2= 3
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triple bond

It is diamagnetic because of the paired electrons

MOLECULAR ORBITAL

EXAMPLES – HETERONUCLEAR (2S)

 Atomic orbitals coming from different elements, have different energies.

 Examples include the HF, CO molecules etc

Bond order = (B e- __ Anti-b e-)/2

= (8-2)/2= 2
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double bond

It is diamagnetic because of the paired electrons

MOLECULAR ORBITAL

EXAMPLES – HETERONUCLEAR (2S)

Draw the molecular orbital diagram of the HF molecule

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