CHAPTER 9: MOLECULAR GEOMETRY AND BONDING

THEORIES

PRE-TEST
A. Fill in the blanks. Choose the right answer from the box.

1. A ___________, a geometric object with four corners and four faces each an
equilateral triangle.
2. With the help of bond ______ we can determine the shape of a molecule.
3. In VSEPR Model, VSEPR stands for? _______________________________
4. Octahedron has _______ faces, which are all equilateral triangles.
5. _______________ is a measure of how equally the electrons in a bond are
shared between the two atoms of the bond.
6. The _______ model means for predicting molecular geometries but does not
explain why bond exists between atoms.
7. The process of mixing atomic orbitals in a mathematical operation is called
______________.
8. ___________ have more than an octet of electrons around the central atom.
9. A type of covalent bond with a line joining the two nuclei that passes through
the middle of the overlap region is called ______ bond.
10. A ___ bond is one in which the overlap regions lie above and below the
internuclear axis.
B. Matching type. Name the following figure in column A by choosing the right
answer from the column B.

A B
____ 1. a. Tetrahedral
____ 2. b. Linear

____ 3. c. Trigonal Planar

____ 4. d. Octahedral

____ 5. e. Bent

____ 6. f. Trigonal Pyramidal

____ 7. g. Trigonal Bipyramidal

____ 8. h. Lewis Structure

____ 9. i. T-shaped

____ 10. j. Sea-saw

9.1 Molecular Shapes

Molecular Geometry, also known as molecular structure, is the three-dimensional

structure or arrangement of atoms in a molecule. Understanding the molecular structure of
a compound can help determine the polarity, reactivity, phase of matter, color, magnetism,
as well as biological activity. The shape of a molecule is determined by its bond angles,
the angles made by the lines joining the nuclei of the atoms in the molecule. The bond
angles of a molecule, together with the bond lengths, define the shape and size of the
molecule.

Molecular geometry gives information about the general shape of the molecule as
well as bond lengths, bond angles, torsional angles, and any other geometrical parameters
that determine the position of each atom.

Types of Molecular Geometry

A. Linear
⮚ In this structure, two molecules are attached to the central
atom. So they arranged in the opposite direction in order to
minimize their repulsion.
⮚ The bond angle of this structure is 180°.
⮚ Example: BeCl2, MgCl2 etc.

B. Trigonal Planar
⮚ In this type of molecule, we find three molecules attached to
a central atom. So, they are arranged toward the corners of an
equilateral triangle in order to minimize their repulsion.
⮚ The bond angle of this structure is 120°.
⮚ Example: BF3, BCl3, AlF3 etc.

C. Tetrahedral
⮚ In a tetrahedral molecular geometry, a central atom is located
at the center with four substituents that are located at the corners
of a tetrahedron.
⮚ The bond angle of the structure is 109°28’.
⮚ Example: CH4, CCl4, etc.
 D. Trigonal Bipyramidal
⮚ In a trigonal bipyramid, three positions lie along the equator
of the molecule. The two positions lie along an axis
perpendicular to the equatorial plane.
⮚ The bond angle are 90°and 120°.
⮚ Example: PF5

E. Octahedral
⮚ It describes the shape of compounds with six atoms
or groups of atoms or ligands symmetrically arranged around
a central atom, defining the vertices of an octahedron.
⮚ The bond angle is 90°.
⮚ Example: SF6, TeF6 etc.
Other Examples of Molecular Shapes:
Name Molecular Shape

a. Bent

b. Pyramidal

c. Sea-saw
 d. T-shaped

e. Square Pyramidal

f. Square Planar

Various spectroscopic methods and diffraction methods can determine the

molecular geometry. IR, microwave, and Raman spectroscopy can give information about
the molecule geometry from the details of the vibrational and rotational absorbance
detected by these techniques. X-ray crystallography, neutron diffraction, and electron
diffraction can give molecular structure for crystalline solids based on the distance between
nuclei and concentration of electron density.

Several methods have developed to determine the distance between the various atoms in a
molecule and the angle in the bond involved. However, the geometries and observed shape of the
covalent molecules can be predicted theoretically with the help of the Valence Shell Electron Pair
Repulsion Theory or the VSEPR Theory.
9.2 VSEPR Model

The VSEPR Model or Valence Shell Electron Pair Repulsion Model (pronounced
“vesper”). It is used to predict the shape of the molecules from the electron pairs that
surround the central atoms of the molecule. The theory was first presented by Sidgwick
and Powell in 1940. The VSEPR theory assumes that the molecule will take shape such
that electronic repulsion in the valence shell of that atom is minimized.

According to this model, valence electrons in the Lewis structure form groups,
which may consist of a single bond, a double bond, a triple bond, a lone pair of electrons,
or even a single unpaired electron, which in the VSEPR model is counted as a lone pair.
Because electrons repel each other electrostatically, the most stable arrangement of
electron groups (i.e., the one with the lowest energy) is the one that minimizes repulsions.
A bonding pair of electrons thus defines a region in which the electrons are most likely to
be found. We will refer to such a region as an electron domain. Likewise, a nonbonding
pair (or lone pair) of electrons, defines an electron domain that is located principally on
one atom.

In the VSEPR model, the molecule or polyatomic ion is given an AX E designation,

where A is the central atom, X is a bonded atom, E is a nonbonding valence electron group
(usually a lone pair of electrons), and m and n are integers. Each group around the central
atom is designated as a bonding pair (BP) or lone (nonbonding) pair (LP). From the BP
and LP interactions we can predict both the relative positions of the atoms and the angles
between the bonds, called the bond angles. Using this information, we can describe the
molecular geometry, the arrangement of the bonded atoms in a molecule or polyatomic
ion.

In determining the shape of any molecule, we first use the VSEPR model to predict
the electron-domain geometry. We must remember that molecular geometry involves only
electron domains due to bonds even though the nonbonding pairs contribute to the electron-
domain geometry.
Steps We Follow in Using the VSEPR Model to Predict the Shapes of Molecules or
Ions:

1. Draw the Lewis structure of the molecule or ion and count the number of electron
domains around the central atom. Each nonbonding electron pair, each single bond,
each double bond, and each triple bond counts as one electron domain.
2. Determine the electron-domain geometry by arranging the electron domains about
the central atom so that the repulsions among them are minimized.
3. Use the arrangement of the bonded atoms to determine the molecular geometry.

Example 1.
Use the VSEPR model to predict the molecular geometry of (a) O3, and (b) SnCl3.

(a) O3
Step 1. Lewis Structure.
⮚ Because of resonance, the bonds between the central O atom and the outer
O atoms are of equal length. In both resonance structures the central O atom
is bonded to the two outer O atoms and has one nonbonding pair.

Step 2. The Electron-Domain Geometry.

⮚ Thus, there are three electron domains about the central O atoms.
Remember that a double bond counts as a single electron domain. The
arrangement of three electron domains is trigonal planar. Two of the
domains are from bonds, and one is due to a nonbonding pair.

Step 3. The Molecular Geometry.

⮚ So, the molecular geometry is bent with an ideal bond angle of 120°

(b) SnCl3.
 Step 1. Lewis Structure.

Step 2. The Electron-Domain Geometry.

Step 3. The Molecular Geometry.

⮚ So, the molecular geometry is trigonal-pyramidal.

9.3 Molecular Shape and Molecular Polarity

Now that we have a sense of the shapes that molecules adopt and why they do so,
we will return to some topics that we first discussed namely, bond polarity and dipole
moments. Recall that bond polarity is a measure of how equally the electrons in a bond are
shared between the two atoms of the bond. As the difference in electronegativity between
the two atoms increases, so does the bond polarity.

The dipole moment of a diatomic molecule is a measure of the amount of charge

separation in the molecule. It is denoted by the Greek Letter 𝜇. Bond dipoles and dipole
moments are vector quantities; that is, they have both a magnitude and a direction. The
dipole moment of a polyatomic molecule is the vector sum of its bond dipoles. Both the
magnitudes and the directions of the bond dipoles must be considered when summing
vectors. Dipole moments are experimentally measurable and are usually reported in debyes
(D), a unit that equals 3.34 × 10-30 coulomb-meters (C-m). For molecules, we usually
measure charge in units of the electronic charge 𝑒, 1.60×10-19 C, and distance in angstroms.
This means we need to convert units whenever we want to report a dipole moment in the
debyes. Suppose that two charges 1+ and 1- (in units of 𝑒) are separated by 1.00 Å. The
dipole moment produced is
 A Polar Molecule is a molecule that has a net dipole as a result of the uneven
distribution of electrons between the covalently bonded atoms. Polar molecules are formed
when there is a difference between the electronegativity values of the atoms participating
in a bond.

A Nonpolar Molecule is a molecule whose charge distribution is spherically

symmetric when averaged over time. This means that the electrical charges of nonpolar
molecules are evenly distributed across the molecule.

Example 2.
Predict whether these molecules are polar or nonpolar: (a) BrCl, (b) SO2, (c) SF6.

(a) BrCl
⮚ Chlorine is more electronegative than bromine. All diatomic molecules with
polar bonds are polar molecules. Consequently, BrCl is polar, with chlorine
carrying the partial negative charge:
The measured dipole moment of
(b) SO2 BrCl is = 0.57 D.
⮚ Because oxygen is more electronegative than sulfur, SO2 has polar bonds.
Three resonance forms can be written:

⮚ For each of these, the VSEPR model predicts a bent molecular geometry.
Because the molecule is bent, the bond dipoles do not cancel, and the
molecule is Polar:

⮚ Experimentally, the dipole moment of SO2 is μ = 1.63 D.

(c) SF6
⮚ Fluorine is more electronegative than sulfur, so the bond dipoles point
toward fluorine. For clarity, only one S¬F dipole is shown. The six S¬F
bonds are arranged octahedrally around the central sulfur:
 ⮚ Because the octahedral molecular geometry is symmetrical, the bond
dipoles cancel, and the molecule is Nonpolar, meaning that 𝜇 = 0.

Polar and nonpolar molecules containing polar bonds. The numbers are
electronegativity values.

9.4 Covalent Bonding and Orbital Overlap

The VSEPR model provides a simple means for predicting molecular geometries
but does not explain why bonds exist between atoms. This situation refers to the process in
which the two atoms come so close to each other that they penetrate each other’s orbital
and form a new hybridized orbital where the bonding pair of electrons reside. This
hybridized orbital has lower energy than the atomic orbital and hence are stable. It is in the
minimum energy state. This partial penetration of the orbital is known as orbital overlap.
The overlap of bonding orbitals is substantially increased through a process called
hybridization, which results in the formation of stronger bonds.

The Valence Bond Theory is an extension of Lewis’s notion of electron-pair

bonds. In valence-bond theory, covalent bonds are formed when atomic orbitals on
neighboring atoms overlap one another. The overlap region is one of greater stability for
the two electrons because of their simultaneous attraction to two nuclei. The greater the
overlap between two orbitals, the stronger the bond that is formed.

Example: The H2 molecule

 The simplest case to consider is the hydrogen molecule, H2. When we say that the
two electrons from each of the hydrogen atoms are shared to form a covalent bond between
the two atoms, what we mean in valence bond theory terms is that the two spherical 1s
orbitals overlap, allowing the two electrons to form a pair within the two overlapping
orbitals. In simple terms, we can say that both electrons now spend more time between the
two nuclei and thus hold the atoms together. As we will see, the situation is not quite so
simple as that, because the electron pair must still obey quantum mechanics - that is, the
two electrons must now occupy a shared orbital space. This will be the essential principle
of valence bond theory.

These two electrons are now attracted to the positive charge of both of the hydrogen nuclei,
with the result that they serve as a sort of ‘chemical glue’ holding the two nuclei together.

Bond Distance and Energy

If they are too far apart, their respective 1s orbitals cannot overlap, and thus no
covalent bond can form - they are still just two separate hydrogen atoms. As they move
closer and closer together, orbital overlap begins to occur, and a bond begins to form. This
lowers the potential energy of the system, as new, attractive positive-negative electrostatic
interactions become possible between the nucleus of one atom and the electron of the
second. However, something else is happening at the same time: as the atoms get closer,
the repulsive positive-positive interaction between the two nuclei also begins to increase.
 At first, this repulsion is more than offset by the attraction between nuclei and
electrons, but at a certain point, as the nuclei get even closer, the repulsive forces begin to
overcome the attractive forces, and the potential energy of the system rises quickly. When
the two nuclei are ‘too close’, we have a very unstable, high-energy situation. There is a
defined optimal distance between the nuclei in which the potential energy is at a minimum,
meaning that the combined attractive and repulsive forces add up to the greatest overall
attractive force. This optimal internuclear distance is the bond length. For the H2 molecule,
this distance is 74 x 10-12 meters or 0.74 Å (Å means angstrom, or 10-10 meters). Likewise,
the difference in potential energy between the lowest state (at the optimal internuclear
distance) and the state where the two atoms are completely separated is called the bond
energy. For the hydrogen molecule, this energy is equal to about 104 kcal/mol.

Although we tend to talk about "bond length" as a specific distance, it is not

accurate to picture covalent bonds as rigid sticks of unchanging length - rather, it is better
to picture them as springs that have a defined length when relaxed, but which can be
compressed, extended, and bent. This ‘springy’ picture of covalent bonds will become very
important, when we study the analytical technique known as infrared (IR) spectroscopy.

9.5 Hybrid Orbitals

When the valence bond theory was unable to accurately predict molecular structure,
hybridization was developed to explain it. According to experimental findings, the bond
angles of organic molecules are near to 109o, 120o, or 180o. The Valence Shell Electron
Pair Repulsion (VSEPR) theory states that electron pairs resist one another and that bonds
and lone pairs around a core atom are typically spaced at the greatest angles.

Carbon is a perfect example showing the value of hybrid orbitals. Carbon's ground
state configuration is:
 Given that it possesses two unpaired electrons in its electrical configuration, carbon
should make two covalent bonds to produce a CH2 according to the Valence Bond Theory.
However, tests have revealed that CH2 is very reactive and cannot exist without a reaction.
This does not explain how CH4 may occur, therefore. The arrangement of carbon requires
four unpaired electrons in order to create four bonds.

One way CH4 can be explained is, the 2s and the 3 2p orbitals combine to make
four, equal energy sp3 hybrid orbitals. That would give us the following configuration:

The four unpaired electrons that carbon now possesses allow it to form four bonds
with equal energies. Hybridized orbitals are more directed, which causes higher overlap
when bonds are formed and, as a result, stronger bonds. This is why it is advantageous for
orbitals to become hybridized. When this happens, hybridization produces more stable
molecules.

The next section will explain the various types of hybridization and how each type
helps explain the structure of certain molecules.

sp³ hybridization
Tetrahedral structure of molecules can be accounted for via sp3 hybridization. In it, the two
2s orbitals and all three 2p orbitals combine to generate four sp3 orbitals, each of which
has a p character of 75% and a s character of 25%. The alignment of the frontal lobes is
depicted in the image below. The amount of electron repulsion is reduced in this
arrangement.
 Energy changes occurring in hybridization

Hybridization of an s orbital with all three p orbitals (px , py, and pz) results in four
sp3 hybrid orbitals. sp3 hybrid orbitals are oriented at bond angle of 109.5o from each other.
This 109.5o arrangement gives tetrahedral geometry (Figure 4).

Example: sp3 Hybridization in Methane

We shall use carbon as an example because it is crucial to understanding organic
chemistry. Four sp3 orbitals are created when the 2s and all three of the 2p orbitals of
carbon combine. Through an overlap of the sp3 and s orbitals, these orbitals subsequently
form a link with four hydrogen atoms to form methane. Since this minimizes electron
repulsion, the final form is tetrahedral.

Hybridization
Lone Pairs: Lone electron pairs should be taken into consideration. Since these lone pairs
are unable to form double bonds, they are given their own hybrid orbital. H2O is tetrahedral
due to this reason. If we look beyond s and p subshells, we can construct sp3d and sp3d2
hybrid orbitals as well.

sp² hybridization
The sp2 hybridization process can be used to explain molecules' trigonal planar
structure. It produces three sp orbitals, each of which has a 67% p and 33% s character,
through the hybridization of the two 2p orbitals and the two 2s orbitals. To reduce electron
repulsion and increase overlap, the frontal lobes arrange themselves in the trigonal planar
configuration, pointing to the corners of a triangle. The final p orbital is parallel to the plane
formed by the three sp2 orbitals and is unaltered.

Energy changes occurring in hybridization

Hybridization of an s orbital with two p orbitals (px and py) results in

three sp2 hybrid orbitals that are oriented at 120o angle to each other (Figure 3).
Sp2 hybridization results in trigonal geometry.

Example: sp2 Hybridization in Aluminum Trihydride

One 2s orbital and two 2p orbitals combine to generate three sp2 orbitals in
aluminum trihydride, which line up to form the trigonal planar structure. Through the
overlap of their sp2-s orbitals, the three Al sp2 orbitals are able to bind with the three
hydrogens' 1s orbitals.
Example: sp2 Hybridization in Ethene

Each carbon in ethene undergoes a comparable hybridization. One 2s orbital and

two 2p orbitals combine to generate three sp2 orbitals for every carbon atom. The trigonal
planar structure is where these hybridized orbitals line themselves. Through s-sp orbital
overlap, two of these sp orbitals form a bond with two 1s hydrogen orbitals for each carbon
atom. Each carbon bonds to the other through the overlap of its remaining sp2 orbitals,
creating a link between each carbon. The two p orbitals on each carbon that contain a single
carbon are what are left.
sp hybridization

Hybridization helps explain how molecules have linear structures. It produces two
sp orbitals, each of which has 50% s and 50% p character, through the hybridization of the
2s orbital and one of the 2p orbitals. The front lobes create a straight line facing away from
one another, forming a 180° angle between the two orbitals. Electron repulsion is reduced
by this creation. We are left with two unaffected 2p orbitals that the atom can employ
because only one p orbital was used. These p orbitals are perpendicular to the line created
by the two sp orbitals as well as to one another.

Energy changes occurring in hybridization

Figure 1: Notice how the energy of the electrons lowers when hybridized.

In compounds like ethyne, where they make two addition, these p orbitals are
relevant. the formation of a triple bond. This only occurs when two atoms, like two carbon
atoms, both have two p orbitals with one electron each. Figure 2 shows what happens when
a s orbital and a p orbital merge to form a sp hybrid orbital. Due to the fact that we began
with two orbitals (s and p), we will obtain two sp hybrid orbitals. As a result of sp
hybridization, two directional sp hybrid orbitals that point in different directions are
produced. Higher electron densities in the bonding region are produced by these hybridized
orbitals for a sigma bond to the left of the atom and another sigma bond to the right.
Additionally, linear geometry with a 180o bond angle is provided via sp hybridization.

Example: sp Hybridization in Magnesium Hydride

The 3s orbital from magnesium and one of the 3p orbitals hybridize to generate two
sp orbitals in magnesium hydride. The two frontal lobes of the sp orbitals form a straight
line facing away from one another, creating a linear configuration. Through sp-s orbital
overlap, these two sp orbitals are joined to the two 1s orbitals of the two hydrogen atoms.

Hybridization

Example: sp Hybridization in Ethyne

Ethyne hybridization is comparable to magnesium hydride hybridization. The 2s
orbital combines with one of the 2p orbitals on each carbon atom to create two sp
hybridized orbitals. These orbitals' frontal lobes create a straight line facing away from one
another. The two carbons' sp-sp orbitals overlap to form the initial bond. The sp hybridized
orbitals of the carbon atoms and the 1s orbitals of the hydrogen atoms combine to form two
additional bonds. As a result, we are left with two p orbitals on each carbon that each
contain one carbon.

Hybridization
9.6 Multiple Bonds

A multiple bond is a chemical link between two atoms in chemistry where two or
more electron pairs are shared. Multiple bonds include double and triple bonds.

In contrast to a single bond, which only has two bonding electrons, a double bond
has four. Sulfoxides (S=O), imines (C=N), and azo compounds (N=N) all include double
bonds. A double bond is often indicated by the equal sign.

Six bonding electrons are present in a triple bond. Three parallel lines (≡) are used
to depict the triple bond. Alkynes contain the most prevalent type of triple bond. Triple
bonds (N≡N) are much more powerful than double or single bonds, and molecular
nitrogen (N2) is a prime example.

There are three different kinds of covalent bonds that can form: single bonds,
double bonds, and triple bonds.
Remember: Single bonds are a result of two atoms sharing a pair of electrons.

How are multiple bonds formed?

• Double bonds, result from the sharing of two pairs of electrons between two atoms.
 • Triple bonds, come from the sharing of three pairs of electrons between two atoms.

Double Bonds

Compared to single bonds, double bonds are both stronger and shorter. But
compared to triple bonds, they are weaker and longer.

Triple Bonds

Triple bonds are the strongest and shortest covalent bonds.

Reminder:

The basic components of the group typically follow the octet rule. Atoms' ability to
share valence numbers so restricts the types of bonds they can form.
Example: Oxygen is missing 2 electrons; thus it can only form two single bonds OR one
double bond in order to complete its octet.
9.7 Molecular Orbitals

Many elements of bonding can be explained by valence bond theory, but not all of
them. We employ a second hypothesis known as the molecular orbital (MO) theory to
supplement this one. A more complex model for comprehending the nature of chemical
bonding is molecular orbital theory.

The linear combination of atomic orbitals (LCAO), a mathematical technique used

in MO theory, is used to create new molecular orbitals, taking the concept of atomic orbitals
overlapping to a new level.

Atomic and molecular orbitals are quite similar in many ways:

• According to the Aufbau principle, they are filled from lowest energy to maximum
energy.
• According to the Pauli exclusion principle, they can hold a maximum of two
electrons with opposing spins in each orbital.

Atomic orbitals indicate the electron density in space associated with a certain
atom, whereas molecular orbitals represent electron density in space. The electron density
is delocalized (spread out) over several atoms because molecular orbitals are linked to the
entire molecule.

The Molecular Orbitals of the Hydrogen Molecule

With the use of LCAO, two molecular orbitals σ1s (pronounced "sigma one s") and
σ*1s (pronounced "sigma star one s")—are produced by combining the 1s orbitals of each
hydrogen atom.

The two atomic orbitals' wave functions combine (or interact) constructively to
create the s orbital, which they reinforce (add to). The bonding molecular orbital, which
has the lower energy of the two molecular orbitals, is what it is called. The electron density
of this orbital is centered between the two nuclei, as seen in the "Hydrogen molecular
orbital combination diagram" in Figure 9.19. These electrons form a covalent link between
the atoms and stabilize each other by being attracted to both nuclei.

The destructive combination (or interference), in which the wave functions of the
two atomic orbitals cancel each other out, produces the σ*1s orbital. The area between the
two nuclei that results from this kind of combination is called a nodal plane (or node) and
has a zero electron density. The term "antibonding molecular orbital" (indicated by the
asterisk in the orbital name) refers to this type of orbital, which is destabilizing toward
the bond and raising its energy.

Figure 9.19 “Hydrogen molecular orbital combination diagram.”

For molecular orbitals, electron configuration energy diagrams can be written in a

manner similar to that of atomic orbitals (see Figure 9.20, "Hydrogen molecular orbital
electron configuration energy diagram"). The freshly formed molecular orbitals are printed
in the center of the diagram, and you'll notice that each atom's atomic orbitals are written
on either side. H2 molecules are more stable than hydrogen atoms on their own because the
bonding molecular orbital is filled and has a lower energy than the contributing atomic
orbitals.
 Figure 9.20 “Hydrogen molecular orbital electron configuration energy diagram.”

Bond Order

The creation of a covalent bond is encouraged by the bonding molecular orbital,

which has lower energy, whereas the antibonding molecular orbital, which is higher energy
and has a node of zero electron density between the atoms, destabilizes the formation of a
covalent link. The bond order of a covalent bond can be used to gauge its strength.

Values for the bond-order can be zero, whole numbers, or fractions. A bond order
of 1 corresponds to a single bond, whereas a bond order of 2 corresponds to a double bond,
according to the valence bond model. If the value is zero, there is no link and the atoms are
independent.

Example 9.11

Determine the bond order of the hydrogen molecule.

Solution

Therefore there is a single bond in the hydrogen molecule.

Molecular Orbitals of Li2

Following a few additional rules is necessary when using the LCAO method to create
molecular orbitals of molecules other than hydrogen.

• The total number of atomic orbitals plus the number of MOs produced equals the
number of MOs.
• Atomic orbitals should have equal energies when combined.
• The degree of orbital overlap affects how well atomic orbitals combine. The energy
of the bonding molecule orbital is further reduced as overlap increases, whilst the
energy of the antibonding molecular orbital is increased.

Molecular Orbitals from p Atomic Orbitals

We must consider how p orbitals interact to produce molecular orbitals in order to

ascertain the molecular orbitals of numerous different molecules. The p orbitals may cross
each other directly or indirectly. With the electron density centered along the internuclear
axis, bonding and antibonding molecular orbitals are created when two p atomic orbitals
overlap head-to-head (Figure 9.22, "Head-to-head overlap of p orbitals").
 Figure 9.22 “Head-to-head overlap of p orbitals.”

Sideways overlap of the remaining four p atomic orbitals can occur along the two
other axes, generating four π molecular orbitals having electron density on opposite sides
of the internuclear axis (Figure 9.23 “Sideways overlap of p orbitals”).

Figure 9.23 “Sideways overlap of p orbitals.”

The bonding molecular orbital of an atom with a greater head-to-head overlap has
the lowest energy and is the most stable, whereas the antibonding molecular orbital with a
greater head-to-head overlap has the highest energy (Figure 9.24, "Molecular orbital
energy diagram for homonuclear diatomic molecules made from atoms of atomic number
8-10"). Four molecular orbitals π two lower-energy degenerate-bonding and two higher-
energy antibonding orbitals σ* are produced by sideways overlap.
 Figure 9.24 “Molecular orbital energy diagram for homonuclear diatomic molecules
made from atoms of atomic number 8-10.”

The energy map we just created does not fit for B2, C2, and N2 but fits
experimentally with O2, F2, and Ne2. These subsequent homonuclear diatomic compounds
(B2, C2, and N2) exhibit interactions between the 2s and 2p atomic orbitals that are potent
enough to reverse the ordering of the σ2p and π2p molecular orbitals.
 Figure 9.25 “Molecular orbital energy diagram for homonuclear diatomic molecules
made from atoms of atomic number 5-7.”

Heteronuclear Diatomic Molecules

The energies of the atomic orbitals of the individual atoms may differ in
heteronuclear diatomic molecules, which are composed of two distinct molecules bound
together. However, the electron configuration and bond order can be inferred from the
molecular orbital diagram shown in Figure 9.25 ("Molecular orbital energy diagram for
homonuclear diatomic molecules made from atoms of atomic number 5-7").

Frontier Molecular Orbitals

The highest occupied molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO), commonly referred to as the frontier molecular orbitals jointly
(Figure 9.26 "Frontier molecular orbitals HOMO and LUMO"), are two extremely
significant types of molecular orbitals on which we can concentrate further. The HOMO is
the molecule orbital with the highest energy and electrons, as its name suggests, whereas
the LUMO is the molecular orbital with the lowest energy and no electrons.

Figure 9.26 “Frontier molecular orbitals HOMO and LUMO.”

 A HOMO electron typically uses the energy it receives from absorbing energy to
move from the ground HOMO orbital to the excited-state LUMO orbital. UV-visible (UV-
Vis) radiation spectroscopy investigations can detect this kind of transition. The HOMO
electrons of one reactant molecule may also be transferred to the LUMO of another reactant
in numerous chemical reactions (see Figure 9.27, "Formation of a new bonding molecular
orbital by combining reactant HOMO and LUMO"). As a result, knowledge of frontier
molecular orbital energy levels can help chemists comprehend molecular spectroscopy and
reactivity much better.

Figure 9.27 “Formation of a new bonding molecular orbital by combining reactant

HOMO and LUMO.”

9.8 | Period 2 Diatomic Molecules

Diatomic Molecules
A diatomic molecule is one that contains two atoms. Atoms from the same element
or from distinct elements are also possible. The atoms of a diatomic molecule are united in
a straight line and have a linear shape. At normal temperature, almost all diatomic
molecules are gases.
Types of Diatomic Molecules

There are two types of diatomic molecules – homonuclear and heteronuclear

Homonuclear

If the two atoms in a diatomic molecule are of the same kind, the molecule is said to be
homonuclear. It has the shape A2. The molecule was created via the covalent link between
the two atoms, as shown by the subscript 2, which is 2. Covalent bonds can be single,
double, or triple-stranded and are invariably nonpolar. A diatomic element is another name
for a homonuclear diatomic molecule. The periodic table lists seven of them.
Examples

• Hydrogen (H2)

• Nitrogen (N2)

• Oxygen (O2)

• Fluorine (F2)

• Chlorine (Cl2)

• Bromine (Br2)

• Iodine (I2)
All but bromine and iodine are gases at room temperature. Br2 is liquid, and I2 is solid at
room temperature.

How to Remember the Diatomic Element

All seven of the diatomic elements have a nonmetal and a 'gen' ending. The only elements
that have a 'gen' ending are hydrogen, nitrogen, and oxygen. The other four are halogens.
Have No Fear Of Ice Cold Beer is a simple mnemonic for the diatomic elements.
Heteronuclear

A diatomic molecule is heteronuclear if the two atoms are of different types. The
form of this molecule is A-B. Here, at least one of the atoms is a nonmetal. The bonding in
a heteronuclear diatomic molecule is either covalent or coordinate covalent.

Examples

• Carbon monoxide (CO)

• Nitric oxide (NO)

• Hydrogen fluoride (HF)

• Hydrogen chloride (HCl)

• Hydrogen bromide (HBr)

POST-TEST

A. Encircle the letter of the correct answer.

1. A three-dimensional structure or arrangement of atoms in a molecule.
a. Molecular Chemistry
b. Molecular Botany
c. Molecular Geometry
d. Molecular Biodiversity

2. The angles made by the lines joining the nuclei of the atoms in the molecules that
can determine the shape of the molecule.
a. Bond Angle
b. Ionic Bonding
c. Covalent Bond
d. Linear
3. It describes the shape of compounds with six atoms or ligands symmetrically
arranged around a central atom.
a. Linear
b. Trigonal Planar
c. Octahedral
d. Trigonal Bipyramidal
4. It predicts the shape of the molecules from the electron pairs that surround the
central atom of the molecule.
a. VSEPE Model/Theory
b. VSEPR Model/Theory
c. VSRPE Model/Theory
d. VRSEP Model/Theory
5. A type of pair that refers to a region in which the electrons are most likely to be
found.
a. Bonding Pair
b. Non-Bonding Pair
c. Pro-Bonding Pair
d. Pre-Bonding Pair
6. It measures how equally the electrons in a bond are shared between the two
atoms of the bond.
a. Bond No Polarity
b. Bonding Polarity
c. Bond Polarity
d. Pre-Bond Polarity
7. A molecule that has a net dipole as a result of the uneven distribution of
electrons.
a. Non-Polar Molecule
b. In-Polar Molecule
c. Pre-Polar Molecule
d. Polar Molecule
8. A molecule whose charge distribution is spherically symmetric or evenly
distributed across the molecule.
a. Non-Polar Molecule
b. In-Polar Molecule
c. Pre-Polar Molecule
d. Polar Molecule
9. An extension of Lewis’s notion of electronegativity bonds. Wherein the covalent
bonds are formed when atomic orbitals on neighboring atoms overlap one another.
a. Atomic Bond Theory
b. VSEPR Model/Theory
c. Valence Bond Theory
d. Lewis’s Dot Structure
10. It refers to the optimal internuclear distance.
a. Bond Theory
b. Bond Length
c. Bond Energy
d. Repulsion
REFERENCES

Admin. (2022). Molecular geometry - Definition, Determination, Types, VSEPR

theory and FAQs on molecular geometry. BYJUS; BYJU’S.
https://byjus.com/chemistry/molecular-geometry/

9.2: The VSEPR Model. (2014). Chemistry LibreTexts.

https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_
-
_The_Central_Science_(Brown_et_al.)/09%3A_Molecular_Geometry_and_Bondi
ng_Theories/9.02%3A_The_VSEPR_Model

Kamau, James. “VSEPR Theory - Postulates, Limitations, Predicting Shapes.” BYJUS,

byjus.com/jee/vsepr-theory/.

Molecular Shape and Molecular Polarity. (2023).

https://chem.libretexts.org/@go/page/21753

Ball, D. W., & Key, J. A. (2014). Molecular Shapes and Polarity. Opentextbc.ca;
BCcampus. https://opentextbc.ca/introductorychemistry/chapter/molecular-shapes-
and-polarity/

Chima, H., Yasmeen F. (2013). Hybrid Orbitals. retrieved from

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Or
ganic_Chemistry)/Fundamentals/Hybrid_Orbitals

Expii (N.D). Multiple Bonds - Double & Triple Bonds. retrieved from
https://www.expii.com/t/multiple-bonds-double-triple-bonds-8373

Helmenstine, A, Ph.D. (2019). Multiple Bond Definition in Chemistry. retrieved from

https://www.thoughtco.com/definition-of-multiple-bond-605379

Key, J. (N.D). Molecular Orbitals. retrieved from

https://opentextbc.ca/introductorychemistry/chapter/molecular-orbitals/

Bhuyan, S. (2023) Diatomic Molecules: Definition and List. retrieved from

https://www.chemistrylearner.com/diatomic-molecules.html
ANSWER KEYS
Pre-test
A. B.
1. Tetrahedron 1. Linear
2. Angles 2. Octahedral
3. Valence-Shell Electron-Pair Repulsion 3. Trigonal Pyramidal
4. Eight 4. Trigonal Bipyramidal
5. Bond Polarity 5. Lewis Structure
6. VSEPR 6. Sea-saw
7. Hybridization 7. T-shaped
8. Hypervalent 8. Tetrahedral
9. Sigma or 𝜎 9. Trigonal Planar
10. Pi or π 10. Bent

Post-test
A.
1. C
2. A
3. C
4. B
5. A
6. D
7. D
8. A
9. C
10. B

Nuguid, Lorenzo F.
Longakit, Rovic
BSES-1B