Chemical Bonding

V.B. , M.O. Theories

&
Lewis Concept
 Theoretical Considerations of the
Energetics of Bond Formation
• Electrostatic attraction between atoms - the energetics of bond formation
• Electropositive atoms form metallic bonds.
• Electronegative atoms form covalent bonds
• Electropositive and electronegative atoms form ionic bonds
• A chemical bond forms if, as a result, the energy of the bonded atoms is
substantially lower than that of separate atoms so that the combination can be
detected as a separate unit.
• If the lowest energy can be achieved by ion formation, then the bonding will be
ionic. If the lowest energy can be achieved by electron sharing, then the bonding
will be covalent. Hence, to come to any conclusion about the type of bonding
present in a compound, we must consider the energy changes that accompany
bond formation.
• The Covalent bond
• What are the forces involved, and how do they change when two atoms come
together? How does the energy change as a result?
• Let us consider two hydrogen atoms HA and HB coming towards each other. They
will develop two types of forces:
 Bonding (contd.)
• (a) Repulsive forces
(i) repulsion between the electron of atom HA and the electron of atom HB
(ii) repulsion between the nucleus of atom HA and the nucleus of atom HB.
• (b) Attractive forces
(i) attraction between electron of HA and the nucleus of HB
(ii) attraction between electron of HB and the nucleus of HA.
• The net effect of the interplay of these forces changes as the two atoms come
closer together. To begin with, the attractive forces dominate as HA and HB come
closer to each other and increases till it reaches a maximum. Any further decrease
in internuclear distance would lead to a decrease of attraction till the internuclear
distance reaches a point where net attraction becomes zero beyond which a net
repulsion is observed.
• When the two atoms are brought closer to each other under the influence of
attraction the potential energy decreases. The potential energy reaches a
minimum when the net attraction decrease to zero and the corresponding
internuclear distance corresponds to the average bond length. (N.B. it is the
average bond length since each bond keeps on increasing and decreasing in length
Potential Energy variations in Bonding

The figure 1(a) shows the variations of the net interatomic force and figure 1(b)
shows the potential energy variation with changing internuclear distance and
are self explanatory. The energy difference between the energy of two 'free'
hydrogen atoms and the potential energy minimum is known as the bond
dissociation energy.
 Ionic Bond
• The Ionic Bond
• The above description gives a general picture about the energetics of covalent
bond formation where both atoms are electronegative and the resultant bonding
involves a sharing of two electrons.
• If one atom is electropositive and the other electronegative, even then a potential
energy minimum will be seen corresponding to covalent bond formation. Then
why do we have the formation of an ionic bond in such cases?

• If we look at the case of bonding between potassium (K) and fluorine (F), we can
further elaborate on the puzzling situation. The figure 2 sums it up graphically.
At large distance, the potential energy of a neutral (K + F) situation is much lower
than the (K+ + F-) situations. This is because (ionisation energy of K( - )electron
affinity of F) involves an increase in energy from a system containing isolated
gaseous atoms of K and F. However, as the internuclear distance decreases, the
coulombic attraction between K+ and F- gaseous ions starts increasing sharply. The
potential energy curves for the ionic state then crosses the curve for the neutral
state to reach a minimum value, which is much lower than that for the latter.
Ionic Bond(contd.)
 Theories of Bonding
• Valence bond theory and molecular orbital theory - the two theories of bonding.
• To understand the energetics of bonding on the basis of the quantum mechanical
model of the atom, two different theories have been used with distinct
approaches.
• (a) The valence bond theory
Here, to start with, we consider the orbitals of the bonding atoms as one electron
wave functions and then go about combining them before calculating the
electronic energy of the resultant 'bonds'. The essential feature in this approach is
that to start with, we distinguish between electrons belonging to different atoms
and correlate them accordingly.
• According to quantum theory, the electrons in an atom or a molecule are
indistinguishable since they constantly 'exchange' with each other. The valence
bond theory takes care of it by using the concept of resonance where it implies
that the actual "distribution" of electron is a 'resonance hybrid' of all the
different possible "distributions" incorporating all possible types of correlations.
The different "distributions" schemes are referred to as "limiting structures".
 Theories of Bonding (contd.)
• Thus, for the H2 molecule we may consider four limiting structures corresponding
to the correlations
• (i) Atom A - Electron A + Atom B - Electron B (covalent structure)
• (ii) Atom A - Electron B + Atom B - Electron A (covalent structure)
• (iii) Atom A - Electrons A and B (ionic structure)
• (iv) Atom B - Electrons A and B (ionic structure)
• We have mentioned this, since the concept of resonance has been used
extensively in explaining polar covalent bonds and bonding in molecules where the
electrons are delocalized. Another special feature about the valence bond
approach is that it implies an extra stabilization due to electron pairing.
• (b) The Molecular Orbital theory
Here we consider the orbitals as eigenstates in atoms and combine them to form
molecular orbitals before calculating the energies of the latter. Unlike atomic
orbitals, the molecular orbitals belong to the molecule as a whole. After arranging
the molecular orbitals in order of increasing energy, we apply Aufbau principle to
fill them up and obtain a description of the electron distribution in the molecule.
 Theories of Bonding (contd.)
• (c) Theory and practice - the application of bonding theories for studying
chemistry
• Both these theories have their advantages and disadvantages and some of the
concepts we will be using are derived from either one or the other of the theories.
• Most concepts such as resonance, hybridization of atomic orbitals, orbital box
diagrams for electronic configurations, number of bonds, descriptions of bonds
etc. are a direct consequence of the valence bond theory.
• The molecular orbital theory on the other hand has given some approximately
parallel concepts such as bond order instead of the number of bonds; and orbitals
instead of bonds; bonding, antibonding and nonbonding electrons instead of bond
pairs and lone pairs; delocalised molecular orbitals instead of resonance, etc.
 Lewis Structure
• The Lewis Octet Rule (1916) and the Lewis Dot Structure
"A covalent bond is a pair of electrons shared between two atoms."
• Lewis thought that, because the two electrons of a shared pair can attract the
nuclei they lie between them and would pull the two atoms together. The
brilliance of Lewis lay in conjuring up this figure of 'two‘ electrons being shared on
the basis of the knowledge about the number of valence electrons in an atom and
about molecular formulas only. He had no idea about orbitals and the quantum
mechanical model of the atom. Today, we know that in covalent bonding, two
atoms share an orbital which because of Pauli's exclusion principle cannot have
more than two electrons. Lewis had used an empirical rule called the octet rule to
reach his conclusions.
• The Octet Rule
In electrovalent compounds, one atom loses electron whereas the other gains
electrons until both the atoms have reached a noble gas configuration (a duplet in
the valence shell for elements close to helium and an octet for all other elements).
It was Lewis who suggested that atoms could also share electrons until they had
reached a noble gas configuration and expressed this as the octet rule.
 Octet rule & its violation
• Octet Rule:
Atoms proceed as far as possible towards completing their octets by sharing
electron pairs.
• (a) Duplet instead of octet
When hydrogen forms a covalent bond, there is a duplet around the hydrogen
atom. An octet is not possible here, since hydrogen has only one 1s orbital which
cannot have more than two electrons.
(b) Expanded octet
Elements belonging to the third and higher period have vacant low lying 'd'
orbitals which can be used to accommodate electrons in excess of eight.
• (c) Odd electron molecules
In molecules such as NO2 where the total number of valence electrons is odd (N
has 5 and two O have 12 ->total 17). Then at least one of the atoms will have only
seven electrons. Note that none of the atoms can have nine electrons, i.e. more
than an octet (unless in the case of expanded octets as mentioned above)
• (d) Incomplete octets
When elements having less than four electrons form covalent bonds they do not
Less than Octet
More than Octet
Odd electron Molecules
 Lewis Dot Structures
• The Lewis dot structure and the information it conveys
There is something incorrect in the way we have distinguished the electrons of
different atoms by representing them either with dots or crosses. We know today,
that electrons are indistinguishable and we cannot assign any one electron of a
shared pair to a particular atom. Ideally, they should all be represented by dots (or
crosses).
This is precisely what we do in a Lewis structure of any molecule. In the process,
we avoid assigning specific bonded electrons to specific atoms but convey most
other essential information.
• (a) Connectivity
The Lewis structure tells us which atoms in a molecule are connected with which
other atom. e.g. from the Lewis structures of CO2 and N2O.
We can conclude that the connectivities are:
For CO2 O - C - O and not C - O - O
and for N2O N - N - O and not N - O - N.
• (b) Formal charges
In the example of N2O above one of the nitrogen atoms in the given structure
carries a formal positive charge and the other a formal negative charge.
 Lewis Dot Structures (contd.)
• (c) Number of bonding and nonbonding electron pairs
Electrons involved in bonding are called bonding electron pairs, where as
electrons which are not
participating in bonding are called non bonding electron pairs or lone pairs.
e.g. the oxygen atom in H2O has two lone pairs and two bond pairs.
• (d) Number of bonds
The number of bonds between any two atoms is obviously the number of
bonded pairs of electrons between them. With the additional information that if
there are more than one bond between two atoms, the one of them is a sigma
bond and the others are pi bonds, the number of each type of bonds in a molecule
can be determined..
For example, one can tell from the Lewis structure of CO2 given above, that there
are a total of four bonds in the molecule, of which two are sigma bonds and two
are pi bonds.
• HOW TO WRITE LEWIS STRUCTURE OF MOLECULES
A systematic step by step approach to write Lewis structures is as follows:
 Lewis Dot Structures (contd.)
Deciding on Connectivity
1. Structural isomers have different connectivities. To decide on the
connectivities in such cases, we must have experimental data. For example,
C2H6O may have two possible connectivities.
C-C-O and C-O-C
The first is a liquid alcohol and the second a gaseous ether.

2. Some connectivities are ruled out on the basis of octet (or

duplet)considerations. For example, H2O cannot have H-H-O as the connectivity,
since it would mean that the middle hydrogen exceeds its duplet.

3. When more than one oxygen atoms are present in a molecule, we normally
do not have O-O connectivity unless and until it is peroxide (or for e.g. ozone, O3).
Thus, CH3CO2H cannot have H- -C-O-O-H, as the connectivity.
 Lewis Dot Structures (contd.)
4. For oxoacids, the connectivity should show as many O-H bonds as is the
basicity of the acid. For example H3PO3 (a dibasic acid) should have the
connectivity O-PH(O-H)2

5. In some cases however, one has to write down the complete Lewis
structure, in order to determine whether it would lead to a stable
structure. For example, if you start with N-O-N as the connectivity, the
final structure would be something like which of course is improbable.
 Electron Book Keeping

• There are two types of electron counting to be done while writing a Lewis
structure.
• 1. To check whether an octet is complete, incomplete or exceeded.
• 2. To find out how many of the electrons in the octet of an atom belong to the
atom. For this we have to follow two simple rules, which are as follows:
a) Both the electrons in a lone pair of an atom belong to the atom.
b) Only one of the electrons of a bonded pair of an atom, belongs to it, the other
belongs to the atom bonded to it.
• By counting the number of electrons which belong to a bonded atom, formal
charge can be assigned to it, if necessary.
• All that needs to be done is to compare this number with the number of valence
electrons in the neutral free atom.
i) if they are the same, there is no formal charge.
ii) if the electrons on the structure are greater by a number x, there is a formal
charge of x-.
iii) if the electrons on the structure are less by a number x, there is a formal
charge of x+.
 Electron Book Keeping
Let us take some examples of different structures of the molecule CH2N2.
Structure 1.

Carbon has 1 lone pair and 3 bond pairs.

Total electrons in octet = 1 x2 + 3 x2 = 8 octet complete
Number of electrons belonging to C = 1 x2 + 3 x1 = 5
which is, 5 - 4 = 1 more than the valence electrons of C (4)
the formal charge is 1-.
Middle nitrogen has 4 bond pairs.
Total electrons in octet = 4 x2 = 8 octet complete
Electrons belonging to N = 4 x1 = 4
which is, 4 - 5 = -1 or 1 less than valence electrons of N (5)
the formal charge is 1+.
 Electron Book Keeping

The terminal nitrogen also has one lone pair and three
bond pairs as with the carbon. The octet is complete and 5
electrons belong to this nitrogen. The number is equal to
the number of valence electrons of nitrogen and so there
will be no formal charges on this nitrogen.
The final assignment will be
 Electron Book Keeping

All octets are complete.

Terminal carbon has a share of 4 electrons in its outer orbit ( C has 4
electrons in its outer shell) and has no charge.
Middle nitrogen has a share of 4 electrons in outer orbit(one less
than original atom)and has 1+ charge.
Terminal nitrogen has a share of 6 electrons in outer orbit ( N has 5
electrons in its outer shell )and has 1- charge.
Curved Arrows
 Identifying Coordinate Covalent
Bonds
A coordinate covalent bond , as the name suggests, is essentially a covalent bond.
The only difference is, the bond was not formed by the two atoms contributing one
electron each. Instead, one of the atoms has contributed both the electrons.
While counting the electrons belonging to a bonded atom, however, the history of
how the bond was formed does not matter. There the rules are simple, the two atoms
equally share the two electrons of the bond. The donor atom in a coordinate bond
ends up owning one less electron and the acceptor atom ends up owning one extra
electron.
Example 1.
NH3 and BF3 combine to form a coordinate covalent bond, where N is the donor atom
and B is the acceptor atom as shown below:
 Identifying Coordinate Covalent
Bonds
Thus N owns one electron less and has a positive charge and B owns one
extra electron and has a negative charge. We may identify this situation as a
coordinate bond between N and B and depict it as shown below:
 Steric Number
• C-, neutral N and O+ are isoelectronic, i.e they have the same number of electrons
(which is 5) in outer shell and they have identical bonding environment (1 lone
pair and 3 bond pairs). Other similar examples are as follows:
• Neutral C and N+ No lone pair + 4 bond pairs (Steric no. = 4)
• Neutral N and O+ 1 lone pair + 3 bond pairs (Steric no. = 4)
• Neutral O and N- 2 lone pairs + 2 bond pairs (Steric no. = 4)
• Writing the complete Lewis structure and finding the steric number of an atom
To write a complete Lewis structure, these five steps are to be followed:
• 1. Write down the connectivity. 2. Give each atom its due share of electrons.
• 3. Pair up all the electrons. 4. Check and correct octets.
• 5. Assign formal charges.
• The steric number (SN) of an atom is given by SN = number of lone pairs + number
of bonds pairs.
If there is only one bond between two atoms, it is a sigma bond. If there are
multiple bonds between two atoms, then one of them is a sigma bond and the
others are pi bonds and it is counted as only one Bond pair.
 Steric Number
• Some thumb rules, regarding when C, N and O carry a charge and when they are neutral in the
bonded state.
Lone pairs Bond pairs Total Pairs(Steric No.)
• for neutral carbon None 4 4

• for neutral nitrogen 1 3 4

• for neutral oxygen 2 2 4

• for C+ None 3 3

• for N+ None 4 4

• for O+ 1 3 4

• for C- 1 3 4
• for N- 2 2 4

• for O- 3 1 4
Example: O3
Example: NO2+
 Hydrogen Deficiency Index
How to find no. of pi bonds & rings

• The general formula for a open chain hydrocarbon with no pi bond (saturated
hydrocarbon) is CnH2n + 2.
• The number of hydrogen atoms decreases in units of two for every - pi bond. Thus
the general formula for an alkene is CnH2n and for an alkyne it is CnH2n-2. In case of
cyclic compounds, each ring means a decrease of two hydrogen atoms from the
formula of open chain saturated hydrocarbon)
• Thus an index is formulated called hydrogen deficiency index (HDI) of a
hydrocarbon having formula CxHy as HDI = [ (2x + 2)- y] /2
or alternatively HDI = (number of pi bonds) + (number of rings)
For example in C6H6 (benzene) HDI = { [ ( 2x 6) + 2 ] – 6 } /2 = 4
Alternatively in benzene we have 3 pi bonds and 1 ring so HDI = 3+1 = 4
• In case hetero atoms are present, then to get parent hydrocarbon formula
• (i) Remove halogen and replace by a hydrogen atom.
• (ii) Remove oxygen or sulphur - no further adjustment is necessary.
• (iii) Remove nitrogen or phosphorus and remove a hydrogen atom along with it.
• (Similarily if you decrease one carbon atom to step down in the homologous
series, remove one CH2)
 Hydrogen Deficiency Index

For example
Resonance & Conjugation
Resonance & Conjugation
 Resonance & Conjugation
• Molecules with more than One Lewis Structures: Resonance
and Conjugation
• Identifying conjugated electrons in a molecule
• Conjugated electrons can get delocalized. Hence, such electrons must
either be non-bonding electrons or loosely bound – pi bonding electrons.
• There are cases where even – sigma bonding electrons of C-H bond
participate in resonance – called as hyperconjugation or No bond
resonance ( as no bond is shown between C and H in limiting structures.
• For our convenience we will refer to such electrons as mobile electrons.
• In order to get delocalized, there should be some vacant or vacatable
orbital (which is not a vacant orbital but can accept a pair of electron after
some adjustment in another part of the molecule where the mobile
electrons may move to).
• The condition for conjugation is that there must be a gap of one bond
between the mobile electrons, and the vacant or vacatable orbital.
Resonance & Conjugation
Resonance & Conjugation
Resonance & Conjugation
 Resonance & Conjugation
2. Important and unimportant structures
• The actual electron distribution is a resonance hybrid of that
represented by the individual contributing structures. But all the
structures are not equally important. The following set of rules help
to choose the ones which are more important or significant for
explaining the properties of molecules.
• a) Contributing structures in which there is no change in the
number of sigma and pi -bonds respectively are called isovalent
structures. If the numbers are different they are called
heterovalent structures.
Other factors being equal isovalent resonance structures are more
significant than heterovalent structures.
For example,
Resonance & Conjugation
 Resonance & Conjugation
b) Generation of isolated charges in a structure reduces its significance. This is
another reason why the second structure shown for butadiene above becomes
so insignificant. Structures with more than two isolated charges have
insignificant contribution.
c) Heterovalent resonance may give rise to significant structures if it increases
the negative charge (electron density) on the more electronegative atom.
d) Structures where like charges are present close to each other are normally
not significant.
For example, in

The structure II has insignificant contribution because:

i) There are more than two isolated charges
ii) Like charges are crowded close to each other
 Resonance & Conjugation
3. Resonance energy
The stabilization of a molecule because of resonance or delocalization is
called resonance or delocalization energy. This energy becomes large
when:
a) The contributing resonance structures are equivalent. For example, as
in CO32-
 Resonance & Conjugation
b) Larger the number of contributing structures of roughly
comparable energies greater is the resonance energy.
For example, ClO3 - has greater resonance energy than ClO2-

c) Resonance Energy is large if there are (4n + 2) conjugated

pi -electrons in a planar cyclic compound. Here n may have
values 0,1,2,……
etc. For n = 1, we have the well known case of benzene where the extra
resonance stabilization is related to aromaticity.
Aromaticity and aromatic stabilization may be present in compounds
other than benzene and also for other values of n. Some other such
examples of molecules and ions showing aromatic stabilization are
 Resonance & Conjugation
Some other such examples of molecules and ions showing aromatic
stabilization are
 The VSEPR Theory

• Prediction of Shapes and Bond Angles

• The VSEPR or the valence shell electron pair repulsion theory was proposed
initially by Sidgwick and Powell and was later developed by Gilespie.
• The electron pairs in the valence shell of a central atom repel to get as far away
from each other to determine the bond angles and ultimately the shapes of
molecules.
Predicting shapes:
• Electrons around a central atom are two types.
(a) Those involved in bonding with a neighbouring atom called bonding pair or BP.
(b) Those not involved in bonding called lone pair or LP
• For applying VSEPR theory, we do not consider the electrons involved in the
formation of pi -bonds which are always present along with a – sigma bond in a
multiple bonding situation and do not move away from each other due to
repulsion. The sum of these i.e. LP + BP = steric number or SN.
• The steps involved in applying VSEPR theory to determine shapes of molecules are
as follows:
 The VSEPR Theory

Step 1. Find out the steric number from the Lewis structure.
The steric number determines the basic arrangement of
electron pairs as follows:
The VSEPR Theory
 The VSEPR Theory

The table above gives us an idea regarding the group number of the
central atom corresponding to different VSEPR formulas and also tell us
how the sets.
(i) AB2, AB2E, AB2E2, AB2E3
(ii) AB3, AB3E, AB3E2
(iii) AB4, AB4E, AB4E2
(iv)AB5, AB5E and
(v) AB6, AB6E will show variation of shapes within each set.
The VSEPR Theory
The VSEPR Theory
The VSEPR Theory
The VSEPR Theory
 The VSEPR Theory
• Predicting bond angles and explaining variations:
It is clear that if the steric number of two molecules are the same, their bond
angles should have similar values. For example, CH4, NH3 and H2O all have central
atoms with SN = 4. The bond angles are as follows:
• H - C - H in CH4 109o28' (AB4 molecule)
• H - N - H in NH3 107o (AB3E molecule)
• H - O - H in H2O 104.5o (AB2E2 molecule)
• We can also explain the direction of variation using VSEPR theory (one being
greater or less than the other). Lone pairs repel more than bond pairs. Hence, lone
pairs will try to push the bond pairs together and reduce the angle between the
bond pairs. The greater the number of lone pairs, the greater will be the reduction
in bond angles. Thus we have the bond angles in the example above in the order.
AB2E2 < AB3E < AB4
• Note: The VSEPR theory considers only the number of BP and LP. It has no
consideration for the size or electronegativity of the atoms concerned. Hence it
cannot explain the difference in the bond angles of molecules having the same
VSEPR formula.
 Valence Bond Theory
Hybridization and Shapes
• Applying valence bond theory to bonding involving pure orbitals
• Valence bond theory is an extension of the Lewis approach. In brief, the valence
bond theory is the description of bond formation in terms of the merging of the
atomic orbitals in the valence shell of neighboring atoms and of the pairing of the
spins of the electrons that occupy these orbitals. This merging can take place in
two different ways.
1. The sigma bonds
• A sigma bond consists of two electrons in an orbital that has cylindrical symmetry
about the inter-nuclear axis.
• A sigma bond can be formed by the
• 1. overlap of two s orbitals
• 2. end on overlap of a s orbital with a p orbital
• 3. end on overlap of two p orbitals.
• Conventionally the bonding or the inter-nuclear axis is taken as the z-axis. The
resultant orbital must have z-axis as an axis of symmetry if it has to be a sigma
bond. The figures (a) - (c) depict the formation of sigma bonds
corresponding to cases (1) - (3) respectively.
 Valence Bond Theory
Hybridization and Shapes

Note:
1. We will see later that the orbitals involved in sigma bonding need not always
be pure orbitals of constituent atoms.They may also be hybrid orbitals.
2. Sigma bonds are strong and there cannot be more than one -bond between
two atoms.
 Valence Bond Theory
Hybridization and Shapes
2. pi- bonds
A pi-bond consists of two electrons that occupy an orbital that has
two lobes, one on each side of the inter nuclear axis which lies on a
nodal
plane. The pi -bond has a plane of symmetry which is perpendicular
to the nodal plane.
A pi - bond is formed by the sidewise overlap of (usually) two p
orbitals which must be parallel to each other. Since the inter-nuclear
axis or
the z-axis must lie on a nodal plane, there are two ways in which a
pi- bond may be formed.
 Valence Bond Theory
Hybridization and Shapes

Note:
1.pi -bonds are always formed between pure orbitals.
2.pi -bonds are weaker than sigma -bonds since the overlap is less
3. Since pi-bonds are weak, we rarely observe a pi-bond as the only bond
between two atoms. It can be there only if a sigma-bond is also there.
Also the longer the sigma -bond, the weaker is the pi -bond.
4. More than one pi-bond may be there between two atoms.
5. In case of multiple bonds, one of them must be a sigma- bond while the
others must be pi-bonds. Thus in a double bond we have 1 sigma-bond +1pi-
bond and in a triple bond we have 1 sigma-bond + 2 pi- bonds.
6. A pi -bond cannot be formed with an s orbital.
7. pi-bonds may form between p and d orbitals or between two d orbitals
 Valence Bond Theory
Hybridization and Shapes
 Valence Bond Theory
Hybridization and Shapes
The description shown above cannot explain the shapes as predicted by the
VSEPR theory and which are consistent with experimental observation.
• 1. Bond angle in H2O VSEPR prediction 109o28' (actually slightly less due to LP - LP
repulsion) but Experimental value is 104.5o
Prediction based on above V.B. scheme should be 90o (angle between the two p-
orbitals)
• We may explain the angle greater than 90o in terms of repulsion between the H
atom of water which carry fractional charges. But the problem is, how can the
angle between two 'p' orbitals be > 90o?
• (Note: This scheme nicely explains the bond angles in H2S (92o) or H2Te (90o)
meaning that the additional effect of hydrogen – hydrogen repulsion is not
operative in these cases to any great extent)
• 2. Bond angle in BeF2 VSEPR prediction experimental value = 180o.
Since the s orbitals has no directionality associated with it, the above scheme is
incapable of predicting the shape of BeF2
• .
 Valence Bond Theory
Hybridization and Shapes
• Hybridization of orbitals and VSEPR shapes.
The problems highlighted above can be solved using the concept of
hybridization.
1. Hybridization
• The concept of hybridization involves mixing of dissimilar atomic orbitals
followed by redistribution of energies to form new hybrid orbitals of equal
energy.
• The number of hybrid orbitals produced is equal to the number of orbitals
taking part in hybridization. These hybrid orbitals are distributed in
space symmetrically so as to have minimum electron pair - electron pair
repulsion. These hybrid orbitals have shapes in between the
constituent atomic orbitals and they still follow Pauli's exclusion principle
and Hund's rule. The bonds formed by hybrid orbitals are generally
stronger due to greater overlapping.
• The important characteristics of some of the hybridization are given
below:
 Valence Bond Theory
Hybridization and Shapes
 Valence Bond Theory
Hybridization and Shapes
 Valence Bond Theory
Hybridization and Shapes
• Note:
• 1. The relation between VSEPR shapes and shapes predicted due to hybridization is
quite obvious. This is because hybridized orbitals also take care of sigma- bonds
and lone pairs (and not pi -bonds) and are also distributed in space according to
electron pair –electron pair repulsion.
• 2. The determination of hybridization of an atom is very simple since number of
hybridized orbital is equal to the number of valence shell electron pairs which is
equal to steric number.
Steric number Hybridization
2 sp
3 sp2
4 sp3 (or dsp2 e.g, in [Ni (CN)4]2- & [Pt(NH3)2Cl2] )
5 sp3d or dsp3
6 sp3d2 or d2sp3
7 sp3d3
• 3. In some cases, specially in metal complexes, we may also have a square planar
dsp2 hybridization corresponding to a steric number of 4.
 Valence Bond Theory
Hybridization and Shapes

How the combinations of the different wave functions (orbitals) give rise to
the hybridized orbitals of the given shapes?
The 2s and 2p orbitals mix and redistribute to form two new equivalent hybrid
orbitals each having 50% s and 50% p character. This type of hybridization is
called sp hybridization as it involves only one s orbital and one p orbital.
Since the p orbital is directed along one axis and the s orbital is spherical,
both the sp hybrid orbitals must lie along the same axis as that of the p-
orbitals used, and the angle between them must be 180o. Thus BeF2 molecule
should be linear and have zero dipole moment both of which are also
observed.
 Valence Bond Theory
Hybridization and Shapes

In the formation of BF3 or BCl3, B the central atom, has 1s2 2s2, 2px1
electronic configuration. In order to form three equivalent bonds
first we promote one 2s electron to the vacant 2py orbitals and then hybridize 2s
2px and 2py orbitals to get three new equivalent sp2 hybrid orbitals lying in xy
plane and having an angle of 1200 to each other. These hybrid orbitals will have
one third s and two third p character and the type of hybridization is sp2 or
trigonal hybridization. Thus BF3 molecule should be planar and being
symmetrical should have zero dipole moment as is actually observed.
 Valence Bond Theory
Hybridization and Shapes
In CH4 or CCl4 the central atom C has the electronic configuration 1s2, 2s2, 2px1,
2py1 (Hund's rule).

In order to form four equivalent bonds we promote one 2s electron to vacant 2pz
orbital and then hybridize 2s, 2px, 2py and 2pz orbitals to get four new equivalent
sp3 hybrid orbitals distributed in 3 dimensions and having an angle of 109o 28' to
each other. This type of hybridization is sp3 or tetrahedral hybridization as it
results in distribution of hybrid orbitals towards the corners of a regular
tetrahedron. Thus CH4 and CCl4 molecule will be non-planar and still being
symmetrical should have zero dipole moment. This is also observed
experimentally.
 Valence Bond Theory
Hybridization and Shapes
We can in a similar way see how the symmetry of the participating orbitals is
related to the symmetry of the distribution of hybridized orbitals even in
other cases.
 Valence Bond Theory
Hybridization and Shapes
• Experimentally observed bond angles are often different from the standard angles
between hybridized orbitals. We may explain these variations based on: 1. lone
pair repulsion, 2. size of the central atom & 3. electronegativity of the central
atom and hence the polarity of bonds involved.
• How does the angle between hybridized orbitals and the 'size' (or length) of
hybridized orbitals depend on the type of hybridization?
• Notice that as the ’s’ character of the hybridized orbitals decrease, the angle
between the constituent orbitals (which is also the bond angle) also decreases and
the bond angles increases with increasing 's' character e.g. F - Be - F angle (180o)
> F - B - F angle (120o) [Be in BeF2 is sp hybridized 50% 's' character while B in BF3 is
sp2 hybridized 33.33 % 's' character.]
• Another related factor is the 'size' of hybridized orbitals. The ’s’ orbitals are
spherical and shorter than the lobe shaped 'p' or 'd' orbitals. Hence, The size of
orbitals decrease with increasing 's' character of hybridized orbitals
• If the size of a hybridized orbital participating in bonding is smaller (than another)
then, it gives rise to 1. Smaller bond length 2. Higher bond energy and 3.
Higher electronegativity
 Valence Bond Theory
Hybridization and Shapes
Electron deficient molecules and multi-centre bonding
Elements of groups 13 have only 3 valence electrons and hence cannot complete
their octets by forming covalent bonds. Such molecules are called electron deficient
compounds . There are a number of ways in which electron deficient compounds
try to attain stabilisation.
One of them is formation of multicentre bond formation. In this section we will do a
comparative study of all the different methods.
BF3 stabilizes by the p -p 'back donation' of electrons from F to B by resonance.

when we go to AlCl3, both Al as well as Cl belong to a higher period than B and F

respectively. The Al-Cl -bond is much longer than the B-F -bond. The p -p back
bonding in AlCl3 will be far too weak to lead to stabilisation. AlCl3 solves this
problem by forming a dimer involving the coordinate bond formation by bridging
chlorine atoms as shown below:
 Valence Bond Theory
Hybridization and Shapes

There are four electrons which bind the bridging chlorine atoms to the two
aluminum atoms. This may also be 'imagined' as a three centre four electron
bonds.
Three centre two electron bonds is observed in boron hydride. Unlike F, hydrogen
does not have any lone pairs for back bonding.
Hence BH3 cannot be stabilized either in the BF3 manner or in the AlCl3 manner. The
bonding is explained using the concept of
hyperconjugation as follows:
 Valence Bond Theory
Hybridization and Shapes

Another electron deficient molecule which stabilizes in a manner similar to that of

AlCl3 is BeCl2.
BeCl2 forms a polymer instead of a dimer as in the case of AlCl3.
 Molecular Orbital Theory
• Application of the Molecular Orbital Theory: Bonding in Homonuclear Diatomic
Molecules
Molecular orbitals are formed by the linear combination of atomic orbitals (LCAO).
When orbitals of the same atom combine, we saw how we got the concept of
hybridization. When atomic orbitals of neighbouring atoms combine, we get
molecular orbitals.
•
1. Bonding and Anti-Bonding molecular orbitals
When two atomic orbitals combine they may be added to
each other as
If the signs of the amplitudes of and are the same, the resultant
amplitude of the combination would increase in the region of their overlap
between the two nuclei. Having electrons in such an orbital would mean an
increase in electron density between the nuclei. Since this would lead to bonding,
such molecular orbitals are called bonding molecular orbitals (BMO).
 Molecular Orbital Theory
• If the amplitude signs of the two atomic orbitals are opposite in the
region of their overlap, the resultant amplitude of the molecular
orbital becomes zero. If electrons are present in such an orbital, the
electron density between the nuclei will be drastically reduced,
since a node is formed. The effect would be just the opposite of
bonding. Such orbitals are called antibonding molecular orbitals
(ABMO).
• The molecular orbitals formed are labeled as sigma or pi (for
bonding molecular orbitals) and as sigma*or pi* (for anti-bonding
molecular orbitals), depending on whether it has an axis of
symmetry (along the internuclear axis), or a plane of symmetry.
The different types of combinations for s and p orbitals and the
labels used are as follows:
Molecular Orbital Theory

Fig1: Types of molecular orbitals formed by various

combinations of atomic orbitals.
 Molecular Orbital Theory

• 2. Energies of molecular orbitals

A bonding molecular orbital has a lower energy than the
constituent atomic orbitals, whereas an anti-bonding molecular
orbital has a higher energy.
The different types of and molecular orbitals formed by the
combination of atomic orbitals of elements of 1st and the 2nd
period, and their relative order of energies are given in the figure 2
(a)-(b)

• Fig. 2(a)
 Molecular Orbital Theory

Fig.2 (b) Correlation diagram showing energies of atomic orbitals and

the relative order of energies of molecular orbitals formed by linear
combination of atomic orbitals (LCAO) for
(a) period 1 elements Fig. 2(a)
(b) period 2 elements Fig. 2(b)
 Molecular Orbital Theory
• 3. Filling up of the Molecular Orbitals
Given the molecular orbital energies, the electronic configuration of the molecule
may be determined, using Aufbau's principle. The order of filling up of molecular
orbitals is from lower energy upwards as shown in figure 2 and may be written as

Actually the order of energies of molecular orbitals changes, such that

for molecules of atoms having atomic number greater than 7. But that does
not change the final configuration.
 Molecular Orbital Theory
• 4. Electronic Configuration of Molecules: Bond order and Paramagnetism
Bond order is defined as

• If the molecule has unpaired electrons, it will be paramagnetic.

If the bond order is zero or negative, bond formation will not take place, as
it increases the energy of molecule as compared to that of the isolated
atom. If the bond order is positive, it means that the energy of the atoms
in combined form of molecules is lower and such a molecule should be
formed, whether the octet is complete or incomplete. The bond order of
1, 2 or 3 corresponds to a single, double or triple bond respectively. The
greater the bond order, the greater will be the bond dissociation energy
and lesser will be the bond length. Bond order may be fractional also.
 Molecular Orbital Theory
• Bond order and molecular orbital configuration of some simple molecules
a) Hydrogen molecule (H2)
Total number of electrons in 2H atom = 2
Molecular orbital configuration of H2 molecule = sigma 1s2
Bond order 1/2 ( 2-0)= 1 It will exist and will be diamagnetic.
b) Hydrogen molecule ion ( H2+ )
Total number of electrons in = 1
Molecular orbital configuration of H2+ = sigma 1s1
Bond order ½ ( 1-0) = ½ The molecule will exist and will be paramagnetic.
c) Helium molecule (He2)
Total number of electrons in He2 = 4
Molecular orbital configuration of He2 =
Bond order 1/2 (2-2) =0 The molecule will not exist.
d) Helium molecule ion ( He2+ )
Total number of electrons in = 3
Molecular orbital configuration of He2+ =
Bond order ( 2-1 ) = 1/2 The molecule will exist and will be paramagnetic.
 Bond Length

• Bond Length
• Bond length is the average distance between the centers of two
atoms joined by covalent linkage. It is generally expressed in
Angstrom ( 1 A0 = 10-8 cm ) or picometre, pm (1 pm =10-10cm =10-12
m). Generally, the bond length is the sum of atomic or covalent radii
of two atoms bonded together. Bond length therefore depends on:
• (1) Covalent radii of constituent atoms:
For example, HI > HBr > HCl > HF.
• (2) Presence of bonds: A double bond is shorter than a single bond
and a triple bond is shorter than a double bond.
For instance, the bond length in C-C is 1.5 , in C = C it is 1.33 and in C
triple bond C, the bond length is 1.2 .
• (3) Type of Hybridization: Bond length decreases with an increase
in the s character of a hybrid orbital. Thus,
 Bond Length

4. Inductive effect: greater the magnitude of the inductive effect the shorter
will be the bond length.
Thus –I effect of halogens is in the order
Cl > Br > I
hence the C-C bond length is in the order
 Bond Energy
• In the formation of a covalent bond, energy is released. The same energy will be
required to break the bond and is referred to as bond energy. It is a measure of
bond strength. The same bond in a different structural environment will generally
have different bond energy values. Therefore, we use an average of these values
obtained from the study of a large number of compounds having the same bond.
• In diatomic molecules the bond energy may be directly obtained, as the energy
required to break bonds in one mole of the molecule.
• But in polyatomic molecules, for example H2O, the actual bond energies for the
same type of bonds are different for first and second –O-H bonds. Therefore the
bond energy of –O-H bond is taken as an average of the two values. Similarly, in
NH3 the actual N-H bond energies are different and again, an average is taken to
determine the bond energy of N-H. Similarly, in CH4, the four C-H bonds have
different values for bond dissociation energy and an average of these is used as
the bond energy of C-H bond. Thus, bond energy values are an average of the
various values of bond dissociation energies of the same type of bonds present in
the molecule.
 Bond Energy
General considerations:
(1) Bond energy for sigma bond is more than that of pi bond.
(2) Amongst the various sigma bonds formed by hybrid orbitals, the bond energy
increases with increase in the s-character of the hybrid orbital. Thus, the bond
energy of a sigma bond formed by sp-sp overlap is greater than that of a bond
formed by sp2-sp2 overlap which in turn is greater than that of a sp3-sp3 sigma
bond. Similarly, the bond energies of other sigma bonds are in the following order:
sp-sp > sp-sp2 > sp-sp3 or s-sp > s-sp2 > s-sp3
(3) Multiple bonding increases the bond energy i.e. bond energy C-C< C= C < C triple
bond C and N-N < N = N < N triple bond N.
This is due to the presence of additional pi bonds along with a sigma bond.
(4) Generally, the bond energy values decrease as the size of the atom increases.
Thus, H-H > Li-Li >Na-Na > K-K and H-F > H-Cl >H-Br > H-I. Similarly, C-C > Si-
Si > Ge-Ge > Sn-Sn.
But in the series of the group 15, 16 and 17 of the periodic table, the bond
energies are in the following order: Group 15: N-N < P-P > As-As > Sb-Sb
Group 16: O-O < S-S > Se-Se > Te-Te Group 17: F-F < Cl-Cl > Br-Br > I-I
 Bond Energy
• The first member should have the highest bond energy but the bond energies of
these single bonds decrease due to the presence of 1,2 and 3 lone pairs of the
electrons, respectively. But in P-P, S-S and Cl-Cl vacant d-orbitals are available
which can interact with the lone pair on another atom to form p -d bonds. This is
called back bonding and it increases the strength of the bond.
• This is, in fact, responsible for a large number of related interesting facts. The very
low bond energy of F2 is responsible for its high reactivity. The low energy of N-N
or O-O single bonds is the reason why N does not exist as N4 (analogous to P4) and
is not a solid, or why O does not exist as O8 (analogous to S8).
• Similarly, the strength of single C-O is less than than the strength of Si-O because
of the interaction of the lone pair of oxygen with empty d-orbitals of Si which is
not possible in C. This explains why multiple bonding C-O makes CO2 gas, while the
strength of Si-O bond results in a large polymeric network of silica which solidifies.
• The strength of bonds is in the order Al-Cl> Al-Br> Al-I, again because of the
interaction of the lone pair of halogen with the vacant p orbital of Al. This results
in the strength of aluminum halides as Lewis acids to be in the order
AlCl3 < AlBr3 < AlI3.
 Bond Energy
Given below is the table of average bond energies:

• Single bond Single Bond Multiple Bond

( kJ mol-1) ( kJ mol-1) ( kJ mol-1)
• H-H 436 C-F 489 C = C 614
• H-C 413 C-Cl 339 C triple bond C 839
• H-N 391 C-Br 285 C = O 745
• H-O 463 C-I 218 C triple bond N 891
• H-S 367 N-N 163 C = N 615
• H-F 567 N-F 278 N = N 418
• H-Cl 431 N-CI 192 N triple bond N 945
• H-Br 366 O-O 146 O = O 498
• H-I 298 O-F 193
• C-C 348 O-CI 208
• C-N 305 S-S 255
• C-O 358 F-F 159
• C-S 272 CI-CI 242
• Br-Br 193
• I--I 151