CHEMICAL BONDING

DEFINITION

 Chemical Bonding refers to the formation of a chemical bond between two

or more atoms, molecules, or ions to give rise to a chemical
compound. These chemical bonds are what keep the atoms together in the
resulting compound.
 The union of two or more atoms through redistribution of electrons in their
outer most shells involving either transference of electrons from one atom to
another or sharing of electrons amongst themselves so that all the atoms
acquire the stable noble gas configurations of minimum energy.
Ionic Solids or Crystals
Definition:
Solids which are made up of ions and the ions are held together primarily by electrostatic force of attraction
between them.
 Ionic Crystal units are ions (anion & cation)
 They are held together by electrostatic force of attraction.
 Size of anion and cation may be different but they are present in equal amounts so as to maintain electrical
neutrality.
 Each ion will be surrounded by number of ions of opposite charge (known as Co-ordination number).
e.g: In NaCl crystal each Na+ ion is surrounded by 6 Cl-ions & each
 CHARACTERISTICS OF IONIC SOLIDS:
 
CRYSTALLINE IN NATURE:
Ionic compounds are crystalline in nature. (proved by x-ray studies).

MELTING AND BOILING POINTS:

High Melting and boiling points due to strong electrostatic force of attraction

CONDUCTANCE OF COMPOUNDS:
 low conductance in solid state due to strong electrostatic force of attraction
 Good conductors in molten or solution form
 
SOLUBILITY:
 Soluble in polar solvents of high dielectric constant
 Insoluble in non- polar solvents
 SOLUBILITY OF IONIC SOLIDS AND SOLVATION ENERGY:

 When an ionic solid is added to a solvent the cation and anion are surrounded by –ve and +ve ends of solvent molecules.

 These surrounding molecules partially neutralize charge of ions and as well act as insulating sphere. This insulating
effect is called as Dielectric effect.

 The dipole interaction between ions and solvent molecules in solution is called Solvation (if solvent is water it is
Hydration)

 Energy released during solvation is Solvation energy or Hydration energy.

 E.g: one mole of solute + solvent  one mole of solvated ions + solvation energy
 
 
 FACTORS EFFECTING SOLUBILITY OF IONS

1. Dielectric constant of solvent

 High Dielectric constant decreases electrostatic force of attraction between ions and greater will be solvation energy
and in turn greater will be solubility.
 e.g: Dielectric constant of water =80 so NaCl has greater solubility in water and Dielectric constant of ethyl
alcohol= 24 so NaCl is insoluble in alcohol.
2. Lattice energy
 Lattice energy is defined as the energy released when the correct number of gaseous cations and gaseous anions are
brought together from infinite distance to form one mole of an ionic solid.
c+(g) + a- (g)  c+a- + energy released (lattice energy)
cation anion
 Lattice energy is also defined as the energy required to remove ion of one mole of ionic solid from their equilibrium
position in the crystal to infinity.
c+ a- (solid)+energy required  c+(g) + a- (g)
cation anion
Coulomb’s law, F = q1q2/r2
Higher the charges and smaller the distance between the ions, greater is the electrostatic attraction between
them. Hence lattice energy is high and greater is the strength of the ionic bond.
Lattice energy, Mg2+>Li+>Ba+

 Smaller the lattice energy greater will be the tendency of an ionic solid to dissolve.
Lattice energy α 1/solubility
 POLARISATION OF IONS (OR) POLARISING EFFECT (POLARISING POWER) 
Polarization of ions (or) Polarizing effect (polarizing power)
 Ionic bond in a compound like c+ a- is considered to be 100% ionic but in reality it also has some covalent nature.
Similarly, a covalent bond has some ionic character. A bond intermediate between an ionic and a covalent occurs
through a phenomenon known as polarization of ions. It results in a high electron charge concentration between
the two nuclei.

 This partial covalent nature of ionic bond was explained by Fajan.

 According to Fajan the nature of bond between the ions depends upon the effect of one ion on other.

 When two oppositely charged ions approach each other closely the cation tends to attract the outer electrons of the
anions same time it tends to repel the positively charged nucleus of the anion which results in distortion of anion (or)
in other words the anion is polarized. This is known as polarizing effect. The cation is said to be cause of polarization
and the anion is said to be polarized.
 Anion can also cause similar effect on cation. But due to smaller size of cation than anion the polarization of cation
is lesser or negligible.

  A bond intermediate between an ionic and a

covalent bond is called “polar covalent bond”.
 FAJAN’S RULE: RULES REGARDING POLARISATION.
(Factors affecting polarization of ions)
1. Charge on ions
a. Cation: As positive charge on cation increases tendency to attract electrons also increases. Polarizing power of
cation increases.
e.g: AlCl3 > MgCl2 > NaCl
Polarizing power of Al+3 > Mg+2 >Na+
b. Anion: Polarizability of anion increases with increase in negative charge on anion. Because they can repel
their outer electron easily due to large size.
e.g: O2- is more polarized than F-
2. Size of ions
a. Cations with smaller size has greater polarizing power. Due to greater concentration of positive charge on
small surface area.
e.g: polarizing power of Li+ > Na+ > K+ > Rb+ > Cs+
b. The anion with larger size have high polarizability. The nuclear influence on the orbital electrons is weak.
e.g: I- > Br- > Cl- > F-
3. Electronic configuration of cation:

 Cation with 18e- (ns2p6d10) in outer most shell has greater polarizing power than the one with
8e- (ns2p6) even though both may have same size and charge.
As 18e- shell (d electron) shield the nuclear charge less effectively than s and p electron of
8e- shell.
e.g: AgCl more covalent than NaCl
Ag+ ---18e- (greater polarizing power than Na+ 8e- in outer most shell)
 APPLICATIONS AND IMPORTANCE OF FAJAN’S RULES

1. Small polarization — Ionic bond

High polarization-- covalent bond
Intermediate polarization -- partial covalent bond
2. Greater the polarizing power
 Greater the covalent character of compound
 Greater the tendency of cation to form complexes
 Greater will be the tendency to form hydrated salts.

3. Increase in size of anion increases polarizability, which increases acidic nature e.g: HI > HCl

4. As Polarizing power increases, melting point decreases.

5. As polarizing power increases, solubility in polar solvents decreases due to increase in covalent character.

6. Increase in polarization, increases bond energy.

 VALENCE BOND THEORY
The valence bond theory was proposed by end
• Valence bond theory was proposed by Hitler and London to explain the formation of covalent bond
quantitatively using quantum mechanics.
Later on, Linus Pauling improved this theory by introducing the concept of hybridization

• Valence Bond theory describes covalent bond formation as well as the electronic structure of molecules.
• explain the formation of covalent bond
• The theory assumes that electrons occupy atomic orbital's of individual atoms within a molecule, and that the
electrons of one atom are attracted to the nucleus of another atom's
r
• A covalent bond is formed by the overlapping of two half filled valence atomic orbital's of two different atoms.

• The orbitals participating in overlap must have electron with opposite spin.

• The electrons in the overlapping orbital's get paired and confined between the nuclei of two atoms.le

• The electron density between two bonded atoms increases due to overlapping. This confers stability to the molecule
(attain a stable electronic configuration).
• nc
• Greater the extent of overlapping, stronger is the bond formed.
• The direction of the covalent bond is along the region of overlapping of the atomic orbital's i.e., covalent bond is
directional.

• The number of bonds formed by an atom is usually the same as the number of unparied electrons in the ground
state (lowest energy state).

• Some exception is there. If any atom is being excited then the electron which were paired in the ground state are
unpaired and promoted into suitable empty orbitals. Hence, this increases number of unpaired electron as well as
number of bonds.

• Lone pair of electrons: electrons in the valence shell of the original atom which are paired.
 There are two types of covalent bonds based on the pattern (way) of overlapping as follows.
σ-bond
A sigma bond (symbol: σ) is a covalent bond formed via linear overlap of two orbital's.

π-bondA pi bond (symbol: π) is a covalent bond

A pi bond (symbol: π) is a covalent bond formed via parallel overlap of two orbital's.ed parallel
overlap of two orbital's.

The shape of the molecule is determined by the σ bonds ( & lone pairs) but not by the π bonds. π bonds only
shorten the bond lengths.
Wave function:

According to quantum mechanics, Electron : either particles or waves.

So, electrons in an atom may be described as occupying an atomic orbital or by a wave function (ψ).
The wave function for two electrons system (according to the Valence Bond Theory),

ψ(1,2) = ψA(1) ψB(2) or ψA(2) ψB(1)

• Because, electrons are indistinguishable.

• So, both wave functions are equally probable.
• Hence, the (unnormalized) VB wave function for the two electrons system (say hydrogen molecule)

ψA-B(1,2) = ψA(1) ψB(2)  ψA(2) ψB(1) [Addition (+): Symmetrical and Subtraction (-): Unsymmetrical]

Thus, the (unnormalized) VB wave function for an A-B bond is:

ψA-B(1,2) = ψA(1) ψB(2) + ψA(2) ψB(1)

 ψA = Wave function of atom A

 ψB = Wave function of atom B and e(1) and e(2) represents two electrons.

electron in an atomic orbital is custody of one nucleus

 HYBRIDIZATION AND SHAPES OF MOLECULES
DEFINATION:
• The phenomenon of intermixing of atomic orbitals and formation of new orbitals of equal energy is known as
Hybridization.

 Number of hybrid orbitals produced by mixing is equal to number of pure orbitals mixed during hybridization.
• Wave functions of hybrid orbitals made up from a linear combination of all atomic wave functions centered on the
same atom
TYPES OF HYBRIDIZATION

sp Hybridization : LINEAR

sp2 Hybridization : TRIGONAL PLANAR

sp3 Hybridization : TETRAHEDRAL

sp3d Hybridization : TRIGONAL BI PYRAMIDAL

sp3d2 Hybridization : OCTAHEDRAL

sp3d3 Hybridization : PENTAGONAL BIPYRAMIDAL

 sp Hybridization

• It involves the mixing of one s and one p orbital to produce two identical orbitals called sp hybrid
orbitals.
• 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 a sp hybridized orbital.

• sp hybridization is also called diagonal hybridization.

• Each sp hybridized orbital has an equal amount of s and p character, i.e., 50% s and p character.
Examples of sp Hybridization:
•All compounds of beryllium like BeF2, BeH2, BeCl2
•All compounds of carbon-containing triple Bond like C2H2.
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
orbital. The new orbitals formed are called sp2 hybrid orbitals.
 
• hybridization is also called trigonal hybridization.

• It involves mixing of one ‘s’ orbital and two ‘p’ orbital’s of equal energy to give a new hybrid orbital known as sp 2.

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

• All the three hybrid orbitals remain in one plane and make an angle of 120° with one another. Each of the hybrid
orbitals formed has 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 trigonal planar shape.
Examples of sp2 Hybridization
•All the compounds of Boron i.e. BF3, BH3
•All the compounds of carbon containing a carbon-carbon double bond, Ethylene (C2H4)
   Boron trichloride (BCl3)

* The electronic configuration of 'B' in ground state is

1s2 2s2 2p1 with only one unpaired electron. Since the formation of
three bonds with chlorine atoms require three unpaired electrons, there
is promotion of one of 2s electron into the 2p sublevel by absorbing
energy.
Thus Boron atom gets electronic configuration: 1s2 2s2 2px12py1. 
However to account for the trigonal planar shape of this
BCl3 molecule, sp2 hybridization before bond formation was put
forwarded.
* In the excited state, Boron undergoes sp 2 hybridization by using
a 2s and two 2p orbitals to give three half filled sp 2 hybrid orbitals
which are oriented in trigonal planar symmetry. 

* Boron forms three σsp-p bonds with three chlorine atoms by using

its half filled sp2 hybrid orbitals. Each chlorine atom uses it's half filled
p-orbital for the σ-bond formation. 
* Thus the shape of BCl3 is trigonal planar with bond angles equal
to 120o.
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 orbital, 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 109.280

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

sp3d Hybridization

• sp3d hybridization involves the mixing of 1 s, 3 p orbitals and 1 d orbital to form 5 sp3d 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° plane of the equatorial orbitals known as axial
orbitals.
• Example: Hybridization in Phosphorus pentachloride (PCl5)
sp3d2 Hybridization

• sp3d2 hybridization has 1 s, 3 p and 2 d 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° to one another.

sp3d3 Hybridization

• sp3d3 hybridization has 1 s, 3 p and 3 d orbitals, that

undergo intermixing to form 7 identical sp3d3 hybrid
orbitals.

• All 7 orbitals are not equivalent 5 are directed

towards vertices of regular pentagon. Bond angle is
72°.

• Other 2 directional perpendicular to plane of first set

of orbitals and bond angle is 90°.

• The molecule has Pentagonal bipyramidal shape

Hybridization in Ammonia –NH3

N- 1s2,2s2,2p3
7

•  There four sp3 hybrid orbitals of nitrogen atom of  ammonia is formed by the overlapping of three half filled p-
orbitals with filled s-orbital.
• 3 half filled sp3 hybrid orbitals of nitrogen atom are overlapped with s-orbital of 3 hydrogen atoms to form 3 
bond. There remains one full-filled sp3 hybrid orbital.

• Geometry of  ammonia is pyramidal or distorted tetrahedral  due to presence of lone pair. There is lp-bp and
 bp-bp repulsion.
 
Hybridization in water –H2O

O- 1s2,2s2,2p4
8
 
• There are four sp3 hybrid orbitals on oxygen atom . Water  is formed by the overlapping of two half filled sp3 hybrid
orbital of oxygen atom and s orbital of  two hydrogen atom. There remain two full filled sp3 hybrid orbital on oxygen
atom.

•  Geometry of  water  is V-shaped or distorted tetrahedral  due to lp-lp , lp-bp , bp-bp repulsion. The bond angle is 104.50.
 
Hybridization video https://youtu.be/MYLyC89d0t0

Drawbacks of Valence Bond Theory:

1) Valence bond theory is clearly an approximation.

2) It fails to explain certain features of bonding in many simple molecules.

3) Does not explain the magnetic properties of the molecule. e.g. experimentally, molecular oxygen has two
unpaired electron i.e. it is paramagnetic compound. But VB theory can not be explained that.
 MOLECULAR ORBITAL THEORY
 Atomic orbitals combine to give rise to Molecular orbitals.
 Number of atomic orbitals overlapping is equal to number of molecular orbitals formed i.e., if 2 atomic orbitals
overlap then 2 molecular orbitals are formed.
 Out of two molecular orbitals formed one will have lesser energy than sum of both atomic orbitals, this is called as
Bonding Molecular Orbital (BMO).
 The other Molecular orbital will have higher energy than the sum of atomic orbitals this is called anti-Bonding
Molecular orbital (ABMO).
 Like atomic orbital, molecular orbitals also obey Aufbau’s Principle, Hund’s rule, Pauli’s exclusion principle.
 Similar to Atomic orbital, Molecular orbital of lesser energy will be filled first followed by Molecular orbital of higher
energy.

 Electrons entering the orbitals should have anti-parallel spins.

 Electrons occupy the degenerate (of same energy) molecular orbitals singly before they get paired up.
 Each electron in a molecular orbital belongs to all the nuclei in the molecule.

An electron in an atomic orbital is influenced by one nucleus only whereas, an electron in a MO is influenced
by all the nuclei of atoms combined in a molecule  
 
 
 LINEAR COMBINATION OF ATOMIC ORBITAL(LCAO)
 According to LCAO, the molecular orbital wave function is a linear combination of the wave function of
individual atomic orbital, ψA and ψB.

ψMO = i(Ciψi), where Ci is mixing coefficient of atomic orbitals ψi

• As, n number of atomic orbitals should give n MOs,

• Possible wave functions for simple case as (H2 molecule): [ψAB = N(C1ψA  C2ψB),
If A and B are same, then C1 = C2]
ψ = N(ψA  ψB), where, N = normalizing factor

 Bonding orbital is that which is formed by addition (or) symmetrical overlap.

ψb = ψA + ψB ----------- 1

 Anti-bonding is that which is formed by subtraction (or) unsymmetrical overlap.

ψa = ψA - ψB -------------------2

 ψ – the amplitude of the wave function

 ψb – wave function for symmetrical (or) bonding combination.
 ψa – wave function for asymmetrical (or) anti-bonding combination.
 Square of the wave function gives the probability of finding an electron at any point in space.

 Square of eq.-1
ψb2 = (ψA + ψB )2
 

=
ψA2 + ψB2 + 2 ψA ψB ------- 3

 ψb2 gives the probability of finding an electron in

Bonding molecular orbital.
 Its value is greater than the probability of finding an
electron in individual orbital in a molecule A & B.
ψb2 > ψA2 + ψB2 by a factor 2 ψA ψB

Probability of locating an electron in molecular

orbital ψb is greater and has lesser energy than
either of atomic orbitals and leads to formation of
Chemical bond and this is called Bonding
molecular orbital (BMO).
 Square of eq.-2
 
ψa2 = (ψA - ψB )2
 

=
ψA2 + ψB2 - 2 ψA ψB --------4

ψa2 < ψA2 + ψB2 by a factor -2 ψA ψB

 
• Probability of locating an electron in
Anti bonding molecular orbital ψa is
lesser than individual atomic orbitals.
• This Molecular orbital has higher
energy than either of the combining
orbitals and can’t form a stable bond.
So it is called Anti Bonding molecular
orbital (ABMO).
 ψa

  = stabilization energy
----------------------------
 For H2 molecule, a saving of energy is 2
ψA ψB It is only because the system is stabilized in this way
and hence a bond is formed.
ψb ψa

For He2 molecule, there is no saving of energy

and hence He2 does not exist. This situation
corresponds to non-bonding.
ψb
 MODES OF OVERLAPPING

The covalent bond may be classified into two types depending upon the types of overlapping:
(i) Sigma(σ) bond
(ii) pi(π) bond 
Sigma(σ) bond : This type of covalent bond is formed by the end to end (head-on) overlap of bonding
orbitals along the internuclear axis. This is called as head on overlap or axial overlap. This can be formed by
any one of the following types of combinations of atomic orbitals.

 s-s overlapping : In this case, there is overlap of two half filled s-orbitals along the internuclear axis as shown below :

σ*s-s g stands for gerade (even): sign of the wave

ψa = ψA - ψB (ψu) function is unchanged when the orbital is
reflected about its center

u stands for ungerade (odd): sign of the wave

σs-s function is changed when the orbital is
ψb = ψA + ψB
(ψg) reflected about its center
 s-p overlapping: This type of overlap occurs between half filled s-orbitals of one atom and half filled p-
orbitals of another atom.

σs-p
(ψg)

σ*s-p
(ψu)

 p–p overlapping : This type of overlap takes place between half filled p-orbitals of the two approaching
atoms.
  σp-p
ψb = ψA + ψB
(ψg)

ψa = ψA - ψB σ*p-p
(ψu)
pi(π ) bond:
In the formation of π bond the atomic orbitals overlap in such a way that their axes remain parallel to
each other and perpendicular to the inter-nuclear axis. The orbitals formed due to sidewise overlapping
consists of two saucer type charged clouds above and below the plane of the participating atoms.

ψa = ψA - ψB *p-p

(ψg)

ψb = ψA + ψB p-p

(ψu)
Conditions for the combination of Atomic orbitals to form MOs:

• The energy of the AOs should not be differ much from one another.

• The AOs combine only if they overlap to a considerable extent.

• The AOs should have the same symmetry about the molecular axis.

Rules for adding electrons to MOs:

• The molecular orbital with the lowest energy is filled first.

• The maximum number of electrons in molecular orbital cannot exceed two and the two electrons must be of
opposite sign.

• If there are two degenerate molecular orbitals pairing of electrons will occur only after each degenerate
molecular orbital has one electron.
 BOND ORDER

 This is defined as one-half the difference between the number of bonding electrons and the number of antibonding
electrons.

 Bond order = ½ (Nb-Na)

 Bond order 1,2 and 3 signifies single, double and triple bond.

 Bond order is directly proportional to bond dissociation energy and inversely proportional to bond length.
 ORDER OF ENERGY

 Order of energy upto nitrogen where the atomic number is smaller and difference between 2s and 2p orbitals
will be smaller. Therefore, (s-p) mixing occurs and σ2pz orbital has higher energy π2py and π2px.

 σ1s < σ*1s < σ2s < σ*2s < π2py= π2px < σ2pz< π*2py= π*2px < σ*2pz

 As the atomic number increases the energy difference between orbitals increases and therefore mixing is not
possible and σ2pz has lower energy than π2py and π2px.
 
 σ1s < σ*1s < σ2s < σ*2s < σ2pz< π2py= π2px < π*2py= π*2px < σ*2pz

MAGNETIC PROPERTIES

 If all the electrons are paired up, then the molecule is Diamagnetic.

 Presence of unpaired electrons it is Paramagnetic.

 MOLECULAR ORBITAL ENERGY LEVEL DIAGRAMS
OF HOMONUCLEAR DIATOMIC MOLECULES
 

H2
H- 1s1
H- 1s1
H2 = σ1s2
 As bond order is one it is stable molecule.

 Since number unpaired electron it is Diamagnetic.

 
 He2+

He – 1s2
He -1s1 (As it is He2+)
He2+ = σ1s2 < σ*1s1
 Bond order = ½ (Nb-Na)

 Bond order = ½ (2-1)

= ½ (Unstable)

 Paramagnetic
N2
N - 1s22s22p3

N - 1s22s22p3
Energy order – σ1s2 σ*1s2 σ2s2 σ*2s2 π2py2 = π2px2 σ2pz2
 
 Bond order = ½ (Nb-Na)
 Bond order = ½ (10-4)
= 3 (Stable)
Diamagnetic
O2
O - 1s22s22p4
O - 1s22s22p4
Energy order –
σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2py2 = π2px2 π*2py1 = π*2px1
 Bond order = ½ (Nb-Na)
 Bond order = ½ (10-6)
= 2(Stable)
 Paramagnetic
O -
2 (Superoxide ion, e.g. KO2)

O - 1s22s22p4
O - 1s22s22p4
Total electrons =16+1= 17 electrons
Energy order –
σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2py2 = π2px2 π*2py2 = π*2px1
 Bond order = ½ (Nb-Na)
 Bond order = ½ (10-7)
= 1.5 (Unstable) (intermediate between a single

& a double bond)

 Paramagnetic
O -2
2 (peroxide ion, e.g. Na2O2)

O - 1s22s22p4
O - 1s22s22p4
Total electrons =16+2= 18 electrons
Energy order –
σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2py2 = π2px2 π*2py2 = π*2px2
 Bond order = ½ (Nb-Na)
 Bond order = ½ (10-8)
= 1 (Stable)
 Diamagnetic
 F2
F - 1s22s22p5
F - 1s22s22p5

Energy order –
σ1s2 σ*1s2 σ2s2σ*2s2 σ2pz2 π2py2 = π2px2 π*2py2 = π*2px2

 Bond order = ½ (Nb-Na)

 Bond order = ½ (10-8)
= 1 (Stable)

• Diamagnetic
 MOLECULAR ORBITAL ENERGY LEVEL DIAGRAMS OF HETERO NUCLEAR
DIATOMIC MOLECULES

Molecular Orbital diagram of Carbon monoxide molecule (CO):

Total electrons:6 from(C) + 8 from(O) = 14
LUMO
Energy order = σ1s ,σ*1s ,σ2s ,σ*2s , π2py = π2px σ2pz .
2 2 2 2 2 2 2

No: of electrons in bonding molecular orbitals (Nb) = 10

HOMO
No: of electrons in Anti bonding molecular orbital (Na) = 4

• Bond order =1/2(Nb-Na)

=0.5(10-4)= 3
• Stable
• Diamagnetic

• Because of higher electronegativity of oxygen, its AOs are in lower energy than
the corresponding AOs of carbon.
• BMO receive more contribution from AOs of oxygen because of closer to it in
energy HOMO = Highest Occupied Molecular Orbital
• ABMO receive more contribution from AOs of carbon. LUMO = Lowest Unoccupied Molecular Orbital
 Molecular Orbital diagram of CN-

Total electrons:6 from (C) +7 from (N) + 1 =14

Energy order:

σ1s2,σ∗1s2,σ2s2,σ∗2s2,(π2px2​= π2py2​),σ2pz2​
Bond order:

No: of electrons in bonding molecular orbitals (Nb) = 10

No: of electrons in Anti bonding molecular orbital (Na) = 4

• Bond order =1/2(Nb-Na)

=0.5(10-4)= 3

• Stable

• Diamagnetic
 Molecular orbital diagram of NO

Total electrons:7(N) + 8(O) =15

Energy order:
σ1s2,σ∗1s2,σ2s2,σ∗2s2, σ2pz2, (π2px2​= π2py2) π*2py1 = π*2px

Bond order:
No: of electrons in bonding molecular orbitals (Nb) = 10

No: of electrons in Anti bonding molecular orbital (Na) = 5

• Bond order =1/2 (Nb-Na)

=0.5(10-5)= 2.5

• Unstable

• Paramagnetic
 Molecular orbital diagram of NO+

Total electrons:7(N) + 8(O) – 1 = 14

Energy order:

σ1s2,σ∗1s2,σ2s2,σ∗2s2, σ2pz2,(π2px2​= π2py2) ,

No: of electrons in bonding molecular orbitals (Nb) = 10

No: of electrons in Anti bonding molecular orbital (Na) = 4

• Bond order =1/2(Nb-Na)

=0.5(10-4)= 3

• Stable

• Diamagnetic
 Molecular orbital diagram of HF
H - 1s 1

F - 1s22s22p5

• Combination of 1s of H atom and 2s of F atom is not

possible because the energy of 2s of F atom is too low.

• If overlap occurred between 1s of H atom and 2px/2py of

F atom, that would be non-bonding.

• Only the 2pz orbital of F atom combine with 1s orbital of

H atom and yields both bonding ( or sp) and
antibonding ( *or *sp) MOs.

• Two electrons occupy in  MO.

• 2s, 2px and 2py retain their original AO status and called
as non-bonding lone pairs.
Due to the different energies of H (1s) and F (2pz) AOs,
MOs are unsymmetrical.
Energy Order: 2s2 sp2 2px2 2py2

Bond order = (2 – 0)/2 = 1 stable

diamagnetic