Hybridization of Atomic Orbitals

Introduction

Hybridization, in Chemistry, is defined as the concept of mixing two atomic orbitals to give rise
to a new type of hybridized orbitals. This intermixing usually results in the formation of hybrid
orbitals having entirely different energy, shapes, etc. The atomic orbitals of the same energy
level mainly take part in hybridization. However, both fully-filled and half-filled orbitals can
also take part in this process, provided they have equal energy.

On the other hand, we can say that the concept of hybridization is an extension of the valence
bond theory, and it helps us understand the formation of bonds, bond energies and bond lengths.

What Is Hybridization?

The word ‘hybridization’ means ‘mixing’. It is defined as the mixing of atomic orbitals of equal
energy to give new sets of hybridized orbitals. During the process of hybridization, the atomic
orbitals of comparable energies (degenerate orbitals) are mixed together and mostly involves the
merging of two ‘s’ orbitals or two ‘p’ orbitals or the mixing of an ‘s’ orbital with a ‘p’ orbital, as
well as ‘s’ orbital with a ‘d’ orbital. The new orbitals, thus formed, are known as hybrid
orbitals. More significantly, hybrid orbitals are quite useful in explaining atomic bonding
properties and molecular geometry.
NB:
 Atomic orbitals with equal energies undergo hybridization.
 The number of hybrid orbitals formed is equal to the number of atomic orbitals mixed.

 It is not necessary that all the half-filled orbitals must participate in hybridization. Even
completely filled orbitals with slightly different energies can also participate.

 Hybridization happens only during the bond formation and not in an isolated gaseous
atom.

 The shape of the molecule can be predicted if the hybridization of the molecule is known.

 The bigger lobe of the hybrid orbital always has a positive sign, while the smaller lobe on
the opposite side has a negative sign.

Types of Hybridization
Based on the types of orbitals involved in mixing, the hybridization can be classified as sp, sp 2,
sp3, sp3d, and sp3d2. Let us now discuss the various types of hybridization, along with their
examples.

 sp Hybridization

sp hybridization is observed when one s and one p orbital in the same main shell of an atom mix
to form two new equivalent orbitals. The new orbitals formed are called sp hybridized
orbitals. It forms linear molecules with an angle of 180°.

 This type of hybridization involves the mixing of one ‘s’ orbital and one ‘p’ orbital of
equal energy to give a new hybrid orbital known as an sp hybridized orbital.
 The sp hybridization is also called diagonal hybridization.

 Each sp hybridized orbital has an equal amount of s and p characters – 50% s and 50% p
characters.

Examples of sp Hybridization:

 All compounds of Beryllium, like BeF2, BeH2, BeCl2

 All compounds of a carbon-containing triple bond, like C2H2.

Example: In BeF2 Molecule the sp-hybridized orbitals of Be overlap with the half-filled orbitals
of two fluorine atoms to give a linear shape.

sp Hybridisation of BeH2 molecule

  sp2 Hybridization

sp2 hybridization is observed when one s and two p orbitals of the same shell of an atom mix to
form 3 equivalent orbitals. The new orbitals formed are called sp2 hybrid orbitals.

 sp2 hybridization is also called trigonal hybridization.

 It involves the mixing of one ‘s’ orbital and two ‘p’ orbitals of equal energy to give a new
hybrid orbital known as sp2.

 A mixture of s and p orbital formed in trigonal symmetry and is maintained at 1200.

 All three hybrid orbitals remain in one plane and make an angle of 120° with one another.
Each of the hybrid orbitals formed has a 33.33% ‘s’ character and 66.66% ‘p’ character.
  The molecules in which the central atom is linked to 3 atoms and is sp2 hybridized have a
triangular planar shape.

Examples of sp2 Hybridization

 All the compounds of Boron, i.e., BF3 and BH3

 All the compounds of carbon, containing a carbon-carbon double bond, Ethylene (C2H4)

These sp2 hybridized orbitals are oriented at an angle of 120°. When three sp2 hybridized
orbitals of B overlaps with three p-orbitals of fluorine, three σ -bonds are formed with bond
angle 120°. The shape of BF3 molecule is thus trigonal planar.
 Types of Covalent Bonds

Two ways orbitals can overlap to form covalent bonds between atoms are:
 Sigma Bonds (σ):

- end-to-end orbital overlap.

- electron density concentrated between the nuclei of the bonding atoms.

 Pi Bonds (π)
- Sideways orbital overlap.
- electron density concentrated above and below the plane of the nuclei of the bonding atoms.

sp2 Hybridisation of C2H4 molecule

The three sp2 orbitals on each carbon atom form two bonds σ with the two hydrogen; 1s orbitals
and a third σ bond with the sp2 hybrid orbital of the adjacent C atom.
The two unhybridised 2p orbitals of each of the C atoms form a π bond by overlapping sideways.

 sp3 Hybridization

When one ‘s’ orbital and 3 ‘p’ orbitals belonging to the same shell of an atom mix together to
form four new equivalent orbitals, the type of hybridization is called a tetrahedral
hybridization or sp3. The new orbitals formed are called sp3 hybrid orbitals.

 These are directed towards the four corners of a regular tetrahedron and make an angle of
109°28’ with one another.
 The angle between the sp3 hybrid orbitals is 1090.28’

 Each sp3 hybrid orbital has 25% s character and 75% p character.

 Examples of sp3 hybridization are ethane (C2H6) and methane.

Sp3-hybridization: The combination of one s and three p-orbitals to form four hybrid orbitals of
equal energy is known as sp3-hybridization.
Example: Methane (CH4) molecule.

These sp3-hybridized orbitals are oriented at an angle of 109°28'. When these four sp3 hybrid
orbitals overlaps with four 1s orbitals of hydrogen, a symmetrical tetrahedral shaped CH4
molecule form.
 Sp3d Hybridization

sp3d hybridization involves the mixing of 1s orbital, 3p orbitals and 1d orbital to form 5sp 3d
hybridized orbitals of equal energy. They have trigonal bipyramidal geometry.

 The mixture of s, p and d orbital forms trigonal bipyramidal symmetry.

 Three hybrid orbitals lie in the horizontal plane inclined at an angle of 120° to each other,
known as the equatorial orbitals.

 The remaining two orbitals lie in the vertical plane at 90 degrees plane of the equatorial
orbitals, known as axial orbitals.

 Example: Hybridization in phosphorus pentachloride (PCl5)

Sp3d-hybridization: The combination of ones, three p and one d-orbitals to form five hybrid
orbitals of equal energy is known as sp3d-hybridization.
  sp3d2 Hybridization: The combination of ones, three p and two d-orbitals to form six
hybrid orbitals of equal energy is known as sp3d2-hybridization.
- sp3d2 hybridization has 1s, 3p and 2d orbitals, that undergo intermixing to form 6
identical sp3d2 hybrid orbitals.
- These 6 orbitals are directed towards the corners of an octahedron.
- They are inclined at an angle of 90 degrees to one another.

Examples: SF6 Molecule.

 How to determine the type of hybridization?
 Count the number of effective electron pairs around the atom. Effective electron pairs include:
Lone pair. Single bond. Double bond. Triple bond.
Each of the above is counted as one effective electron pair.
Relationship between the number of effective pairs and their hybrid orbitals

No of effective Type of hybridization Arrangement of hybrid

electron pairs orbitals
2 Sp Linear
3 Sp2 Triangular planar
4 Sp3 Tetrahedral
5 Sp3d Triangular bipyramidal
6 Sp3d2 Octahedral

PRACTICE QUESTIONS
1. Predict the hybridization of each atom and describe the molecular Structure. a. CO b. BF4

2. The carbon indicated by the arrow has which of the following hybridizations?

A. sp hybridization B. sp2 hybridization C. sp3 hybridization D. sp3d hybridization

3. In acetylene, how many sigma bonds are present between the two carbons?
A. One B. Two C. Three D. Four
4. The triple bond of 2-propyne contains: A. one sigma bond and one pi bond. B. one sigma bond
and two pi bonds. C. two sigma bonds and one pi bond. D. three sigma bonds.
5. Which of the following represents the arrangement of the sp3 hybrid orbitals in methane?
A. Planar B. Tetragonal planar C. Tetrahedral D. Bipyramidal
6. How many electrons are actually involved in the carbon-carbon bond of acetylene?

7. Which of the following best represents the hydrogen-carbon-hydrogen bond angles in

methane?

8. Give the hybridization states of each of the carbon atoms in the given molecule.
 H2C = CH – CN; HC ≡ C − C ≡ CH; H2C = C = C = CH2
 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY

The VSEPR theory 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 is based on the assumption that the molecule will take shape
such that electronic repulsion in the valence shell of that atom is minimised.

What Is VSEPR Theory?

The Valence Shell Electron Pair Repulsion Theory, abbreviated as VSEPR theory, is based on
the premise that there is a repulsion between the pairs of valence electrons in all atoms, and the
atoms will always tend to arrange themselves in a manner in which this electron pair repulsion is
minimalised. This arrangement of the atom determines the geometry of the resulting molecule.

The different geometries that molecules can assume in accordance with the VSEPR theory can
be seen in the illustration provided below.

VSEPR Theory – Different Geometries That Molecules Can Assume

According to the VSEPR theory, the repulsion between two electrons is caused by the Pauli
exclusion principle, which has greater importance than electrostatic repulsion in the
determination of molecular geometry.

Postulates of VSEPR Theory

The postulates of the VSEPR theory are listed below.

 In polyatomic molecules (i.e., molecules made up of three or more atoms), one of the
constituent atoms is identified as the central atom to which all other atoms belonging to
the molecule are linked.
  The total number of valence shell electron pairs decides the shape of the molecule.
 The electron pairs have a tendency to orient themselves in a way that minimises the
electron-electron repulsion between them and maximises the distance between them.
 The valence shell can be thought of as a sphere wherein the electron pairs are localised on
the surface in such a way that the distance between them is maximised.
 Should the central atom of the molecule be surrounded by bond pairs of electrons, then
the asymmetrically shaped molecule can be expected.
 Should the central atom be surrounded by both lone pairs and bond pairs of electrons, the
molecule would tend to have a distorted shape.
 The VSEPR theory can be applied to each resonance structure of a molecule.
 The strength of the repulsion is strongest in two lone pairs and weakest in two bond pairs.
 If electron pairs around the central atom are closer to each other, they will repel each
other. This results in an increase in the energy of the molecules.
 If the electron pairs lie far from each other, the repulsions between them will be less, and
eventually, the energy of the molecule will be low.

Limitations of VSEPR Theory

Some significant limitations of the VSEPR theory include

 This theory fails to explain isoelectronic species (i.e., elements having the same number
of electrons). The species may vary in shape, despite having the same number of
electrons.
 The VSEPR theory does not shed any light on the compounds of transition metals. The
structure of several such compounds cannot be correctly described by this theory. This is
because the VSEPR theory does not take into account the associated sizes of the
substituent groups and the lone pairs that are inactive.
 Another limitation of the VSEPR theory is that it predicts that halides of group 2
elements will have a linear structure, whereas their actual structure is a bent one.

Predicting the Shapes of Molecules

The following steps must be followed in order to decide the shape of a molecule.

 The least electronegative atom must be selected as the central atom (since this atom has
the highest ability to share its electrons with the other atoms belonging to the molecule).
 The total number of electrons belonging to the outermost shell of the central atom must
be counted.
 The total number of electrons belonging to other atoms and used in bonds with the central
atom must be counted.
  These two values must be added in order to obtain the valence shell electron pair number
or the VSEP number.

What Is the VSEP Number?

The VSEP number describes the shape of the molecule, as described in the table provided below.

Each of these corresponding shapes can also be found in the illustration provided earlier.
However, the VSEPR theory cannot be used to obtain the exact bond angles between the atoms
in a molecule.

Now, we will discuss each shape in detail.

Linear Shape of Molecule

 In this type of molecule, we find two places in the valence shell of the central atom.
 They should be arranged in such a manner that repulsion can be minimised (pointing in
the opposite direction).
 Example: BeF2

Trigonal Planar Shape of Molecule

 In this type of molecule, we find three molecules attached to a central atom.
 They are arranged in such a manner that repulsion between the electrons can be
minimised (toward the corners of an equilateral triangle).
  Example: BF3

Tetrahedral Shape of Molecule

 In two-dimensional molecules, atoms lie in the same plane, and if we place these
conditions on methane, we will get a square planar geometry in which the bond angle
between H-C-H is 900.
 Now, if we consider all these conditions for a three-dimensional molecule, we will get a
tetrahedral molecule in which the bond angle between H-C-H is 109 028’ (toward the
corners of an equilateral triangle) CH4

Trigonal Bipyramid Shape of Molecule

 Let’s take the example of PF 5. Here, repulsion can be minimised by the even distribution
of electrons towards the corner of a trigonal pyramid. 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.

How Can the VSEPR Theory Be Used to Predict the Shapes of Molecules?

The strength of the repulsion between a lone pair and a bond pair of electrons lies in between the
repulsion between two lone pairs and between two bond pairs. The order of repulsion between
electron pairs is as follows:

Lone Pair- lone pair > Lone Pair- bond- pair > Bond Pair- bond pair

1. Total number of electron pairs around the central atom = ½ (Number of valence electrons of
central atom + Number of atoms linked to central atom by single bonds)

 For negative ions, add the number of electrons equal to the units of negative charge on
the ions to the valence electrons of the central atom.
 For positive ions, subtract the number of electrons equal to the units of positive charge on
the ion from the valence electrons of the central atom.

2. The number of bond pairs = The total number of atoms linked to the central atom by single
bonds.

3. Number of lone pairs = The total number of electrons – No. of shared pair

The electron pairs around the central atom repel each another and move so far apart from each
another that there are no greater repulsions between them. This results in the molecule having
minimum energy and maximum stability.

 The shape of a molecule with only two atoms is always linear.

 For molecules with three or more atoms, one of the atoms is called the central atom and
other atoms are attached to the central atom.
 If the central atom is linked to similar atoms and is surrounded by bond pairs of electrons
only, the repulsions between them are similar. As a result, the shape of the molecule is
symmetrical, and the molecule is said to have regular geometry.
 If the central atom is linked to different atoms or is surrounded by bond pair, as well as a
lone pair of electrons, the repulsion between them is similar. As a result, the shape of the
molecule has an irregular or distorted geometry.
 The exact shape of the molecule depends upon the total number of electron pairs present
around the central atom.

Octet Rule
 A stable arrangement is attained when eight electrons surround the atom. This octet can
be made up of its own and some shared electrons. Thus, an atom forms bonds until an
octet of electrons is made. This is known as the octet rule by Lewis. Simply put, the octet
rule refers to the tendency of atoms to prefer eight electrons in the valence shell.
However, d and f electrons are not considered only the s and p electrons are involved in
the octet rule, making it a useful rule for the main group elements (elements not in the
transition metal or inner-transition metal blocks). An octet in this atom corresponds to an
electron configuration ending with s2p6.
 The noble gases rarely form compounds. They have the most stable configuration (full
octet, no charge), so they have no reason to react and change their configuration. All
other elements attempt to gain, lose, or share electrons to achieve a noble gas
configuration.
 Note that there are three exceptions to octet rule, they are:
i. Species with Odd Numbers of Electrons eg. NO (nitrogen monoxide)
ii. Incomplete octet or too few valence electron: Species with incomplete octets are
pretty rare and generally are only found in some beryllium, aluminum, and boron
compounds including the boron hydrides, BH3 (Borane)
iii. Expanded valence shell or too many valence electron. This is more common than
incomplete octet where the central atom in a Lewis structure has more than eight
electrons in its valence shell. In expanded octets, the central atom can have ten
electrons, or even twelve. Molecules with expanded octets involve highly
electronegative terminal atoms, and a nonmetal central atom found in the third
period or below, which those terminal atoms bond to. For example, PCl5 is a
legitimate compound (whereas NCl5) is not

Expanded valence shells are observed only for elements in period 3 (i.e. n=3) and
beyond
 LEWIS STRUCTURE
 Lewis structures (also known as Lewis dot diagrams, electron dot diagrams, Lewis dot
formulas, Lewis dot structures, and electron dot structures) are diagrams that show the
bonding between atoms of a molecule and the lone pairs of electrons that may exist in the
molecule. Lewis structures show each atom and its position in the structure of the
molecule using its chemical symbol. Lines are drawn between atoms that are bonded to
one another (pairs of dots can be used instead of lines). Excess electrons that form lone
pairs are represented as pairs of dots and are placed next to the atoms.
 the diatomic hydrogen molecule (H2) is the simplest model of a covalent bond and is
represented in Lewis structures as:

The shared pair of electrons provides each hydrogen atom with two electrons in its
valence shell (the 1s) orbital. Thereby each hydrogen atoms has the electron
configuration of the noble gas helium (the octet rule).
 When two chlorine atoms covalently bond to form Cl2, the following sharing of electrons
occurs:

Each chlorine atom shared the bonding pair of electrons and achieves the electron
configuration of the noble gas argon.
 In Lewis structures the bonding pair of electrons is usually displayed as a line, and the
unshared electrons as dots

 The sharing of a pair of electrons represents a single covalent bond, usually just referred
to as a single bond. However, in many molecules atoms attain complete octets by sharing
more than one pair of electrons between them:
i. Two electron pairs shared a double bond
ii. Three electron pairs shared a triple bond

N2 is fairly inert, due to the strong triple bond between the two nitrogen atoms and
the N - N bond distance in N is 1.10 Å (fairly short).

Using Octet Rule to Write Lewis Structure

 To write a Lewis structure, we decide on the relative placement of the atoms in the
molecule (or polyatomic ion)—that is, which atoms are adjacent and become bonded to
 each other—and distribute the total number of valence electrons as bonding and lone
pairs.
 Lewis Structures for Molecules with Single Bonds First, we discuss the steps for writing
Lewis structures for molecules that have only single bonds, using nitrogen trifluoride,
NF3, as an example. Step:
1. Place the atoms relative to each other. For compounds of molecular formula ABn,
place the atom with lower group number in the center because it needs more electrons
to attain an octet; usually, this is also the atom with the lower electronegativity. In
NF3, the N (Group 5A; Electronegative (EN) = 3.0) has five electrons and so needs
three, whereas each F (Group 7A; EN = 4.0) has seven and so needs only one; thus, N
goes in the center with the three F atoms around it:

If the atoms have the same group number, as in SO3 or ClF3, place the atom with the
higher period number in the center. H can form only one bond, so it is never a central
atom.
2. Determine the total number of valence electrons available. For molecules, add up the
valence electrons of all the atoms. (Recall that the number of valence electrons equals
the A-group number.) In NF3, N has five valence electrons, and each F has seven:

For polyatomic ions, add one e_ for each negative charge of the ion, or subtract
one e_ for each positive charge.
3. Draw a single bond from each surrounding atom to the central atom, and subtract
two valence electrons for each bond. There must be at least a single bond between
bonded atoms:

Subtract 2e- for each single bond from the total number of valence electrons available
(from step 2) to find the number remaining:

4. Distribute the remaining electrons in pairs so that each atoms ends up with eight
electrons (or two for H). First, place lone pairs on the surrounding (more
electronegative) atoms to give each an octet. If any electrons remain, place them
around the central atom. Then check that each atom has 8e-:

This is the Lewis structure for NF3. Always check that the total number of electrons
(bonds plus lone pairs) equals the sum of the valence electrons: 6e_ in three bonds
plus 20e_ in ten lone pairs equals 26 valence electrons.
This particular arrangement of F atoms around an N atom resembles the molecular
shape of NF3 (Section 10.2). Because Lewis structures do not indicate shape,
however, an equally correct Lewis structure for NF3 is

Or any other that retains the same connections among the atoms—a central N atom
connected by single bonds to three surrounding F atoms.
Using these four steps, you can write a Lewis structure for any singly bonded
molecule whose central atom is C, N, or O, as well as for some molecules with
central atoms from higher periods. Remember that, in nearly all their compounds,
a. Hydrogen atoms form one bond
b. Carbon atoms form four bonds
c. Nitrogen atoms form three bonds
d. Oxygen atoms form two bonds
e. Halogen form one bond when they are surrounding atoms; fluorine is always a
surrounding atom.
Example: write a Lewis structure for CCl2F2, one of the compounds responsible for
the depletion of stratospheric ozone.
Solution.
Step 1. Place the atoms relative to each other. In CCl2F2, carbon has the lowest group
number and EN, so it is the central atom. The halogen atoms surround it, but their
specific positions are not important (see margin).
Step 2. Determine the total number of valence electrons (from A-group numbers): C
is in
Group 4A, F is in Group 7A, and Cl is in Group 7A, too. Therefore, we have

Step 3. Draw single bonds to the central atom and subtract 2e_ for each bond (see
margin). Four single bonds use 8e-, so 32e_ - 8e_ leaves 24e_ remaining.
Step 4. Distribute the remaining electrons in pairs, beginning with the surrounding
atoms, so that each atom has an octet

Counting the electrons shows that each atom has an octet. Remember that bonding
electrons are counted as belonging to each atom in the bond. The total number of
 electrons in bonds (8) and lone pairs (24) equals 32 valence electrons. Note that, as
expected, C has four bonds and the surrounding halogens have one each.
Question: Write a Lewis structure for each of the following
a. H2S (b) OF2 (c) SOCl2
Example 2: write the Lewis structure for methanol, (molecular formula CH 4O), an
important industrial alcohol that is being used as a gasoline alternative in car engines.
Solution
Step 1 . Place the atoms relative to each other. The H atoms can have only one bond,
so C and O must be adjacent to each other. Recall that C has four bonds and O has
two, so we arrange the H atoms to show this
Step 2. Find the sum of valence electrons

Step 3. Add single bonds and subtract 2e_ for each bond (see margin). Five bonds use
10e_, so 14e_ - 10e- leaves 4e_ remaining
Step 4. Add the remaining electrons in pairs. Carbon already has an octet, and each H
shares two electrons with the C; so the four remaining valence electrons form two
lone pairs on O. We now have the Lewis structure for methanol.

Questions: write a Lewis structure for each of the following

a. Hydroxylamine (NH3O) b. dimethyl ether (C2H6O; no O-H bonds)
 Lewis Structure for Molecules with Multiple Bonds: Sometimes, you’ll find that, after
steps 1 to 4, there are not enough electrons for the central atom (or one of the central
atoms) to attain an octet. This usually means that a multiple bond is present, and the
following additional step is needed:
5. Cases involving multiple bonds. If, after step 4, a central atom still does not have an
octet, make a multiple bond by changing a lone pair from one of the surrounding
atoms into a bonding pair to the central atom
Example 3: Write Lewis structures for the following:
(a) Ethylene (C2H4), the most important reactant in the manufacture of polymers (b)
Nitrogen (N2), the most abundant atmospheric gas
Solution
a. For C2H4. After steps 1 to 4, we have
 Step 5. Change a lone pair to a bonding pair. The C on the right has an octet, but the
C on the left has only 6e_, so we convert the lone pair to another bonding pair
between the two C atoms

b. For N2. After 1 to 4, we have

Step 5. Neither N has an octet, so we change a lone pair to a bonding pair
In this case, moving one lone pair to make a double bond still does not give the N on
the right an octet, so we move a lone pair from the left N to make a triple bond

Question: Write Lewis structures for each of the following:

(a) CO (the only common molecule in which C has only three bonds) (b) HCN (c)
CO2
 Resonance (Delocalized Electron-Pair Bonding) structures are a set of two or more Lewis
Structures that collectively describe the electronic bonding of a single polyatomic species
including fractional bonds and fractional charges. Resonance structures are capable of
describing delocalized electrons that cannot be expressed by a single Lewis formula with
an integer number of covalent bonds.

In structure I, ucture I, oxygen B has a double bond to oxygen A and a single bond to
oxygen C. In structure II, the single and double bonds are reversed. These are not two
different O3 molecules, just different Lewis structures for the same molecule. In fact,
neither Lewis structure depicts O3 accurately. Bond length and bond energy
measurements indicate that the two oxygen-oxygen bonds in O3 are identical, with
properties that lie between those of an O-O bond and an O=O bond, something like a
“one-and-a-half” bond. The molecule is shown more correctly with two Lewis structures,
called resonance structures (or resonance forms), and a two-headed resonance arrow
between them. Resonance structures have the same relative placement of atoms but
different locations of bonding and lone electron pairs. You can convert one resonance
form to another by moving lone pairs to bonding positions, and vice versa

Resonance structures are not real bonding depictions: O3 does not change back and forth
from structure I at one instant to structure II the next. The actual molecule is a resonance
hybrid, an average of the resonance forms. We draw the resonance hybrid with a curved
dashed line to show the delocalized pairs:
 Electron delocalization diffuses electron density over a greater volume, which reduces
electron-electron repulsions and thus stabilizes the molecule. Resonance is very common,
and many molecules (and ions) are best depicted as resonance hybrids. Benzene (C6H6),
for example, has two important resonance forms in which alternating single and double
bonds have different positions.

Example: write resonance structure for the nitrate ion, NO3-

Solution
After steps 1 to 4, we have

Step 5. Because N has only 6e-, we change one lone pair on an O atom to a bonding pair
and form a double bond, which gives each atom an octet. All the O atoms are equivalent,
however, so we can move a lone pair from any of the three O atoms and obtain three
resonance structures

 a
VALENCY BOND THEORY
 The basic principle of VB theory is that a covalent bond forms when orbitals of two
atoms overlap and the overlap region, which is between the nuclei, is occupied by a pair
of electrons.
 Valence bond theory, which is built on two assumptions
1. The strength of a covalent bond is proportional to the amount of overlap between
atomic orbitals; that is, the greater the overlap, the more stable the bond.
 2. An atom can use different combinations of atomic orbitals to maximize the overlap of
orbitals used by bonded atoms.
 In valence bonds theory, bonds are considered to form from the overlapping of two
atomic orbitals on different atoms, each orbital containing a single electron
 In order to explain the bonding in organic molecules, however, we will need to introduce
the concept of hybrid orbitals. Valence bond theory is adequate for describing many
aspects of organic structure. In some cases, however, chemists need to use a different
model, called molecular orbital (MO) theory, to talk about covalent bonds in which
electrons are shared not just between two atoms, but between several, or even over an
entire molecule
 Figure shows an electron-pair bond formed by the overlap of two ns atomic orbitals, two
np atomic orbitals, and an ns and an np orbital where n = 2. Maximum overlap occurs
between orbitals with the same spatial orientation and similar energies.

 Limitation of valence bond theory includes:

1. Valence Bond Theory fails to predict dioxygen's paramagnitism; it predicts that
oxygen is diamagnetic. A species is paramagnetic if electrons are not spin-paired and
diamagnetic if the electrons are spin-paired

Molecular Orbital Theory

 In Valence bond (VB) theory, a molecule is pictured as a group of atoms bound together
through localized overlap of valence-shell atomic orbitals. In MO theory, a molecule is
pictured as a collection of nuclei with the electron orbitals delocalized over the entire
molecule. Just as an atom has atomic orbitals (AOs) with a given energy and shape that
are occupied by the atom’s electrons, a molecule has molecular orbitals (MOs) with a
given energy and shape that are occupied by the molecule’s electrons.
 Despite the great usefulness of MO theory, it too has a drawback: MOs are more difficult
to visualize than the easily depicted shapes of VSEPR theory or the hybrid orbitals of VB
theory
Energy Level Diagram
 A bonding molecular orbital is always lower in energy (more stable) than the component
atomic orbitals, whereas an antibonding molecular orbital is always higher in energy
(less stable).
 Molecular Orbital Energy-Level Diagram for H2. The two available electrons (one
from each H atom) in this diagram fill the bonding σ molecular orbital. Because the
energy of the σ molecular orbital is lower than that of the two H 1s atomic orbitals,
the H molecule is more stable (at a lower energy) than the two isolated H atoms
 To describe the bonding in a homonuclear diatomic molecule (a molecule that consists of
two atoms of the same element) such as H , we use molecular orbitals; that is, for a
molecule in which two identical atoms interact, we insert the total number of valence
electrons into the energy-level diagram We fill the orbitals according to the Pauli
principle and Hund’s rule: each orbital can accommodate a maximum of two electrons
with opposite spins, and the orbitals are filled in order of increasing energy
Bond Order
 In the Lewis electron structures, the number of electron pairs holding two atoms together
was called the bond order. In the molecular orbital bond order is the number of electrons
in bonding MOs minus the number in antibonding MOs, divided by two

To calculate the bond order of H, that the σ (bonding) molecular orbital contains two
electrons, while the σ* (antibonding) molecular orbital is empty. The bond order of H is
therefore

 In general, A bond order greater than zero indicates that the molecular species is stable
relative to the separate atoms, whereas a bond order of zero implies no net stability and,
thus, no likelihood that the species will form. In general, the higher the bond order, the
stronger the bond