HYBRID ORBITALS

 In hybridization, the number of hybrid orbitals equals the number of pure

atomic orbitals that combined.

Sp3 hybrid orbitals

 In the case of C, one s orbital and three 2p orbitals hybridize to form four sp3
hybrid orbitals. It is observed that the sp3 hybrid orbitals has two lobes, one
is large and diffused lobe and the other is small. However, only the large
lobe is mostly illustrated for clarity sake.
 The four sp3 hybrid orbitals are tetrahedrally arranged. Thus the CH4 bonds
are formed from the overlap of four sp3 hybrid orbitals with 1s orbital of H.
 H
109.5 ⁰

H H
H
tetrahedrally arranged Overlap of four hydrogens with four
sp3 hybrid orbitals sp3 hybrid orbitals to form CH4.
 The formation of sp3 hybrid orbitals leading to the formation of four C-H
bonds in CH4 by valence bond theory can be explained using a modified
orbital diagram as represented below.

2p
sp3 sp3
2s
HYBRIDIZE BOND
Energy

1s 1s 1s
C atom C atom C atom
(ground state) (hybridized) (in CH4)
Sp2 hybrid orbitals
 sp2 hybrid orbitals are formed from the hybridization of one s orbital and two
p orbitals. The combination of one s orbital and two p orbital produces three
sp2 hybrid orbitals. The remaining unhybridized p orbitals lies perpendicular to
the hybrid orbitals. A typical molecule which forms through sp2 hybrid orbital
is BF3. The formation of BF3 can be described as below:

2p
sp2 sp2
HYBRIDIZE BOND
2s
Energy

1s 1s 1s
B atom (ground state) B atom (hybridized) B atom (in BF3)
 The sp2 hybrid orbitals occupies the shape of a triagonal planar with an angle
of 120⁰ between them.
120 ⁰ F
F
F
Triagonal planar arranged sp2 Overlap of three fluorine with three
hybrid orbitals sp2 hybrid orbitals to form BF3.
sp hybrid orbitals
 When one s and one p orbitals mixes, three set of sp hybrid orbitals are
formed. The remaining two unhybridized orbitals are arranged perpendicular
to the hybrid orbitals. The two sp hybrid orbitals are separated from each
other at an angle of 180 ⁰ thus has a linear geometry. A typical molecule
which forms through sp hybrid orbital is BeCl2. The formation of BeCl2 can be
described as below:
2p
sp sp
HYBRIDIZE BOND
2s
Energy

1s 1s 1s
Be atom (ground state) Be atom (hybridized) Be atom (in BeCl2)
 180 ⁰
Cl Cl

Linearly arranged sp hybrid Overlap of one chlorine with one sp

orbitals hybrid orbitals to form BeCl.
sp3d hybrid orbitals
 sp3d hybrid orbitals are formed when one s orbital, three p orbitals and one d
orbital hybridized. The total number of hybrid orbitals is five. The hybrid
orbitals are arranged in a trigonal bipyramidal geometry.

 The incorporation of the d orbitals in bond formation violates the octet

rule. Thus sp3d hybrid orbitals is an example of an expanded octet
formation.

 An example of a molecule formed from sp3d hybrid orbitals is PCl5.

 P atom (ground state) P atom (excited) P atom (excited)

3d

3p 3p Hybridize sp3d
Excitation

Bond
Energy

3s 3s
sp3d
P atom (in PCl5)
 Cl
Cl

Cl
Cl
Cl
Trigonal bipyramid structure of Overlap of one chlorine with sp3d
sp3d orbitals hybrid orbitals to form PCl5.
sp3d2 hybrid orbitals
 sp3d2 hybrid orbitals are formed when one s orbital, three p orbitals and two
d orbital hybridized. The total number of hybrid orbitals are six. The hybrid
orbitals are arranged in an octahedral geometry.
 The sp3d2 hybrid orbitals is an example of an expanded octet formation.
 An example of a molecule formed from sp3d2 hybrid orbitals is SF6.
 S atom (ground state) S atom (excited) S atom (excited)

3d

3p 3p Hybridize sp3d2
Excitation

Bond
Energy

3s 3s
sp3d2

S atom (in SF6)

 F
F
F
F F
F
Octahedral structure of sp3d2 Overlap of one chlorine with sp3d2 hybrid
orbitals orbitals to form SF6.
FORMATION OF MULTIPLE BONDS
 When an atom undergo sp2 and sp hybridization, it leaves one and two
unhybridized orbitals, respectively.
 Unhybridized atomic orbitals can lead to the formation of multiple bonds.
 Consider the formation of C2H4, ethene, Lewis dot structures illustrates the
formation of double bond between the two carbon atoms.
H ― H

―
― 1 C―
―C 2―
H H
 VBT explains the formation of the double bond using orbitals overlaps. C1
and C2 are bonded to three different atoms, thus are sp2 hybridized.
 The formation of sp2 hybrid orbitals leads to one unhybridized p orbital,
which stands perpendicular to the three sp2 hybrid orbitals.

Unhybridized orbitals

Hybrid orbitals

 Among the three sp2 hybrid orbitals, two overlap with hydrogen orbital and
the remaining one is used to form a bond with the neighboring C atom.

H H
C C
H H
 The unhybridized orbitals on both C atom lie sideways to form another extra
bond, making the bond between the C atoms two.

H H H
H
C C C C
H H H
H
CH2CH2
 In other to differentiate between the two bonds formed between the C
atoms, sigma (σ) is used to designate bonds formed by the overlap of
another orbital through their axis (end-end overlap), whereas pi (π) is used
to designate bond that is formed by the side by side overlap of atomic
orbitals.
Formation of triple bonds
 When an atom undergoes sp hybridization, two hybrid orbitals are formed.
Also two unhybridized orbitals which stand perpendicular to the hybrid
orbitals are left. These unhybridized orbitals can lead to the formation of
triple bonds.
 Consider the case of C2H2. According to Lewis dot structure, its has three
bonds between the carbon atoms. The bond formation can be explained
using the VBT.

H C C H
 The two unhybridized on each carbon also overlap sideways to form two
additional bonds, making the bond between the carbon atoms three. Of this
bonds, one is sigma (σ) bond (end to end overlap) and two are pi bond
(sideways overlap)

H C C H H C C H
MOLECULAR ORBITAL THEORY (MOT)
 In the description of covalent bonds, valence bond theory is useful in
providing significant information about a molecule, especially in the
prediction of molecular geometry.

 However, VBT considers electrons in a molecule to behave as if they reside

in atomic orbitals. This consideration hinders the VBT to account for certain
properties that molecules exhibit.

 For instance, VBT considers O2 to be diamagnetic, but experimental

observation has revealed that O2 is paramagnetic.

 This makes a new theory which accurately describe most of the observed
experimental observation imperative.
 Molecular orbital theory (MOT) describes well the magnetic and other
properties of molecules.

 MOT treats the orbitals in a molecule as a combination of orbitals from the

individual atoms.
 Atomic orbitals are associated with only one atom whereas molecular
orbitals consist of series of orbitals that belong to a molecule as a whole.

 In molecular theory, valence electrons are delocalised over the entire

molecule, not confined to individual atoms or bonds.

 Molecular orbitals (wave functions) arise from adding together

(superimposing) atomic orbitals or wave functions
 A linear combination of atomic orbitals creates molecular orbitals known as bonding and
antibonding orbitals.
 Bonding orbitals arise from a linear combination of atomic orbitals by constructive
interference

 Antibonding orbitals arise from a linear combination of atomic orbitals by destructive

interference.

Principle of molecular orbital theory

 We know that an orbital is a wavefunction. Simply put, electron wave is an orbital.

 So, an overlap of atomic orbitals simply means an overlap of electron waves. Thus if two
hydrogens are overlapping their 1s orbitals to form a bond, it means they are overlapping
their wavefunctions.

 Waves can overlap constructively or destructively.

Constructive interference
 Consider two hydrogens coming together to form H2 molecule. The H atoms
overlaps the 1s orbitals, in theory they overlap their electron waves.
 In a constructive interference, the electron waves from each electron from
each atom add up to obtain a larger overall electron wave as shown below:
Electron wave from H1
H
Electron wave from H2
+
H
Overall electron wave for H2
H
2
 Constructive interference (addition) occurs when electron waves (orbitals) are
in the same phase.
 Because constructive interference is as a result of addition of electron wave
functions, there is greater or an enhanced probability of electron density
between the nuclei of the bonding atoms. Probability density is the likelihood
of finding an electron in the orbital of an atom.

 Thus constructive interference leads to:

 Increased amplitude between nuclei of bonding atoms where they overlap
 Increased probability density between nuclei of bonding atoms
 Decreased or lower energy of electrons in bonding molecular orbitals than
atomic orbitals, hence increases stability of electrons in bonding molecular
orbitals than atomic orbitals.
 The absence of nodal plane along the bond axis.
 Electron probability distribution around molecular orbitals obtained by
constructive interference can be rationalized as below:
 The electron charge will be combination of H1 and H2 and its given by
¿ ¿
 The relation shows that if we add the two electron densities and square it, it
gives the square of the charge density of the individual electron densities plus
an extra charge density (marked in violet).

 Constructive interference places more charge density between the positive

nuclei of the two atoms to reduce repulsion.

 The extra charge density increases the stability of the molecules and reduces
its energy below the 1s orbital as observed in chemical bonding.
 Therefore when there is a constructive interference, the resulting orbital is
referred to as bonding molecular orbital.

(𝟏 𝒔 ¿ ¿ 𝑯 𝟏+𝟏 𝒔 𝑯 )¿
𝟐 Bonding molecular orbital (σ)
Destructive interference
 Aside a constructive interference, two electron waves can overlap in a way
when one is shifted in respect to another. A wave which is shifted in respect
to the other is known as out of phase.
 When two electron waves which are out of phase overlap, it is known as
destructive interference.
Electron wave from H1

Electron wave from H2

Overall electron wave for H2 or

 Because the electron waves are out of phase in a destructive interference,

they cancel (subtract) each other.
 Electron probability distribution around molecular orbitals obtained by
destructive interference can be rationalized as below:

¿ ¿
 The relation shows that if we subtract the two electron densities and square
it, it gives the square of the charge density of the individual electron
densities minus a charge density (marked in violet).

 Therefore destructive interference removes charge density between the

positive nuclei of the two atoms.
 The removal of electron density decreases the stability of the molecule
by increasing repulsion between the nuclei of the hydrogen atoms.
 The increased repulsion increases the energy of the molecular orbital
above that of the 1s orbital.
 Thus destructive interference leads to:
 Decreased amplitude between nuclei of bonding atoms where they
overlap
 Decreased probability density between nuclei of bonding atoms
 Increased energy of electrons in antibonding molecular orbitals than
atomic orbitals, hence decreases stability of electrons in antibonding
molecular orbitals than atomic orbitals.
 The presence of nodal plane between the two nuclei.
 Molecular orbital form through destructive interference is known as
antibonding molecular orbital (*).

(𝟏 𝒔 ¿ ¿ 𝑯 𝟏 −𝟏 𝒔 𝑯 )¿
𝟐 antibonding molecular orbital (*)
 Molecular orbitals can be characterized as pi (π) or sigma (σ) depending on
the mode of overlap of the original orbitals.
 s-orbitals (2s,3s etc.) overlap head on (end-end) to produce sigma bonding
molecular orbitals (σ) and sigma antibonding molecular orbital (σ*).
 p-orbitals on the other hand can form pi(π) bonding molecular orbitals (π)
and π antibonding molecular orbitals when the participating p orbitals
overlap sideways.
 p-orbitals can also form sigma bonding molecular orbitals (σ) and sigma
antibonding molecular orbital (σ*) when the participating orbitals overlaps
head on.

FACTORS THAT DETERMINE ORBITAL INTERACTION

1. The energy difference between the interacting orbitals. The smaller the
energy difference between the two orbitals (preferably like orbitals), the
stronger the interaction. For instance, in the formation Li2, 2s orbital of one
Li will interact with the 2s orbital on the other atom and not the 1s orbital.
2. The magnitude of the overlap. The larger the overlap between the two
orbitals, the stronger the interaction.
DISTRIBUTION OF ELECTRONS IN MOLECULAR ORBITALS
Just like atomic orbitals, the filling of molecular orbitals is also accompanied by
certain rules.
a. The number of molecular orbitals formed is the same as the number of atomic
orbital which combined.
b. Bonding molecular orbitals are of lower energy than the original orbitals.
Antibonding molecular orbital has higher energy than their the original orbitals.
The more stable the bonding molecular orbital, the less stable the
corresponding antibonding molecular orbitals.
c. In ground-state configuration electrons enter first the lowest energy molecular
orbital available.
d. Each molecular orbital can accommodate up to two electrons with opposite
spins according to the Pauli exclusive principle.
e. Electrons enter molecular orbitals of identical energy singly before they pair up.
STABILITY OF MOLECULE AND BOND ORDER
 The stability of molecular species can be determined by calculating their bond
order which is given as:
( 𝒏𝒐 .𝒐𝒇 𝒆 − 𝒊𝒏 𝒃𝒐𝒏𝒅𝒊𝒏𝒈 𝑴𝑶𝒔 ) −(𝒏𝒐 . 𝒐𝒇 𝒆− 𝒊𝒏 𝒂𝒏𝒕𝒊𝒃𝒐𝒏𝒅𝒊𝒏𝒈 𝑴𝑶𝒔)
𝒃𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓 =
𝟐
 The value of the bond can give information about the stability of the molecule.
For instance bond order of one means that there is one covalent bond, hence a
stable molecule.
 Bond order can be fraction, however values of zero or negative means the bond
has negligible stability and the molecule is highly unstable.
 Interpreting the stability of molecules using bond order should be done with
great care as similar bond order obtained from bonding sigma molecular orbital
and bonding pi molecular orbitals may have different properties.
MOLECULAR ELECTRON CONFIGURATION
First period elements
 Lets consider the molecular configuration of a molecule with single electron
H2+ , the electronic configuration can be illustrated as below:
∗
σ 1𝑠

1s 1s
or ¿¿
↿
σ 1𝑠
H H+
𝐇+𝟐¿¿

 The H2+ molecule has only one electron, which is found in the 1s orbital. The
overlap of the 1s orbitals give σ and σ* MOs, the σ bonding MO is filled first
thus contains the single electron as shown in the reduced configuration.
 The electronic configuration of H2, He2+ and He2 can be represented as below
↿ ↿⇂
σ∗
1𝑠
∗
σ 1𝑠 σ∗
1𝑠

1s 1s 1s 1s 1s 1s
↿⇂ ↿⇂ ↿⇂
H σ 1𝑠 H He σ He +
He σ 1 𝑠 He
1𝑠

¿¿ ¿ ¿¿ ¿ ¿ ¿¿ ¿
𝐇𝟐 𝐇𝐞 +¿¿
𝟐
𝐇𝐞 𝟐

 The bond orders for these homonuclear molecules (H2 = 1, He2+ =1/2, He2 =0)
tell that He2 with bond order of 0 (no bond is produced) is unstable compared
to others.
Second period elements
 Let us consider the molecular configuration of diatomic molecules
such as Li2, Be2, B2, C2, N2, O2, F2 in the second period of the period
table.
 For molecules whose valence electron are in the s-orbitals such as Li2,
and Be2 it is fairly easy to construct the molecular configuration by
overlapping the corresponding 1s and 2s orbitals. ↿⇂
↿ σ∗
2𝑠 ↿ ↿⇂ σ∗
2𝑠 ↿⇂
2s ↿⇂ 2s 2s ↿⇂ 2s
σ 2𝑠 σ 2𝑠
¿ ¿¿ ¿¿ ¿ ¿ ¿¿ ¿¿ ¿ ↿⇂
↿⇂
𝑳𝒊 ↿⇂ ↿⇂ 𝑳𝒊 𝑩𝒆 ↿⇂ ↿⇂ 𝑩𝒆
∗ ∗
σ 1 𝑠 σ 1 𝑠

1s ↿⇂ 1s 1s ↿⇂ 1s
σ 1 𝑠 σ 1 𝑠
 The molecular configuration for molecules comprising atoms with p-
orbitals is a little complex. This is because p-orbitals can overlap end
to end or sideways depending on their orientation, leading to the
formation of σ bonding molecular orbitals and π bonding molecular
orbitals as shown below.
𝒛 𝒛

𝒙 𝒙
𝒚 𝒚 𝒛𝒛

𝒙 𝒙
𝒚 𝒚
(σ) 𝒑𝒚 (𝝅 ) 𝒑𝒛 (𝝅 )
 When two p- orbitals overlap, two π bonds are formed (overlap of
2py and 2pz orbitals) along with one σ bond (overlap of 2px orbitals)
which are obtained through constructive interference.

 The corresponding destructive interference leads to the formation of

two antibonding π* and σ* bonding molecular orbitals.

 The σ bonding have lower energy than the pi bonds so occur at lower
energy than π bonding molecular orbitals.

 If we obey the assumption that orbitals of the same energy interact

strongly than those of different energy. The orbitals diagram of O 2, F2
can be illustrated as below:
 In the description of molecular configuration of diatomic molecules, it is
assumed that atomic orbitals of the same energy level combine to form
molecular orbitals.
 Thus, 1s combines with 1s, 2s combines with 2s.

 However, for some molecule with 2s and 2p (2px, 2py and 2pz) orbitals,
combination is a little complex because the 2s orbital and the 2px of 2p orbitals
are all σ bonds and are located in the same region of space between the nuclei
of the two atoms.

 So the σ2s and σ2px easily combine due to very small energy gap difference to
form a sort of new kind of orbitals which has a percentage of the individual
orbitals. Thus we have a modified σ2s and modified σ2px orbitals. These orbitals
contain fraction of each other