Chapter II

Chemical Bonding and

Molecular Structure
2.1. FUNDAMENTAL CONCEPTS OF CHEMICAL
BONDS
2.1.1. Bond length
• The distance between the nuclei of chemically
bonded atoms is called the bond length.
• Denote: l, d (Å or nm)
1Å = 10-10 m; 1nm = 10-9 m.
• For example:
Bonding Length(Å)
H-H (H2) 0,74
C-H (CH4) 1,09
O-H (H2O) 0,96
 2.1.2. Bond angle
The angle formed by two bonds passing
through the nuclei of atoms participating in a
chemical bond is called the valence or bond
angle
 For example:

=180o
=104.5o
CO2 =107o

H2O
NH3
2.1.3. Bond energy
 The bond energy of a diatomic molecule is the
energy released when a chemical bond between two
isolated atoms in gaseous state was formed.
 The bond energy can be calculated by eV/molecule
or KJ.mol-1 and denoted by E
 Example:
H(g) + H(g)  H-H(g) EH-H = - 431 KJ.mol-1
 The more negative bond energy, the more stable the
bond
 The bond energy is a measure to evaluate the bond
strength
Note: The dissociated energy is equal to the bond
energy in value, but opposite in sign.
+ The dissociated energy is the energy needed to break
the chemical bond of a gaseous molecule into
isolated atoms.
+ To measure bond strength, it can be used the bond
energy or the dissociated energy.
2.2. ELECTRONEGATIVITY- FUNDAMENTAL
TYPES OF CHEMICAL BONDING
2.2.1. Electronegativity (EN):
 EN is the ability of an atom to attract toward itself the
electron pair in a chemical bond.
 Elements with high EN have a greater tendency to
attract bonding electrons pair than do elements with
low EN.
 EN is related to electron affinity and ionization energy.
+ An atom such as fluorine, which has a high electron
affinity (tend to pick up electrons easily), and a high IE
(does not lose electrons easily), will have a high EN
+ Sodium, low electron affinity, low IE, has low EN
 EN is a relative concept, meaning that an element’s
EN can be measured in relation to the EN of other
elements.
 Pauling devised a method for calculating relative EN
of most elements.
 In general, EN increases from left to right across a
period. Within each group A, EN decreases from top
to bottom.
 Note that the transition metals do not follow these
trend.
2.2.2. Fundamental types of chemical bonding
• Forces that hold atoms together
• Ionic bonds are the forces of attraction
between ions
– ions formed by electron transfer
– electrostatic forces
• Covalent bonds are the forces of
attraction between two atoms which are
sharing electrons

9
2.2.2. Fundamental types of chemical bonding
1. The ionic bonding
 The ionic bond is formed when two bonding atoms have
the large difference of EN.
+ The bonded electrons pair are transferred completely to
the atom with higher EN, therefore, the positively and
negatively charged ions are formed
+ These oppositely charged ions attract by electrostatic
force to form an ionic compound (ionic solid).
Example:

Li+ + F- → LiF

2Li + F2 → 2LiF
 2Li+ + O2- → Li2O
4Li + O2 →2 Li2O
2. The covalent bonding
 A covalent bond is formed when two bonded atoms
have the EN difference which is relatively small or
equal to 0.
 Covalent bonds may be polar or nonpolar:
- In a nonpolar bond, the electron pair is shared equally
between two bonded atoms, these two atoms have the
same EN.
* The covalent bonds in all homonuclear diatomic
molecules must be nonpolar.
- In a polar covalent bond: the electron pairs are shared
unequally between two bonded atoms.
* An atom with higher EN attract the electron pair much
more than does an atom with lower EN.
 Example: HF molecule.
+ The EN of F is 4 and that of H is 2.1.
+ Clearly, the F atom, with its higher EN attract
the shared electron pair much more strongly than
does the H atom.
+ H + F → HF
 Molecule F2 : F + F → F2
 Ionic Bonds
• Results from reaction between Metal and Nonmetal
• Metal loses electrons to form cation, Nonmetal gains electrons to
form anion
• Ionic bond is the attraction between a positive ion and negative
ion
• Larger Charge = Stronger Attraction
• Smaller Ion = Stronger Attraction
• No bond is 100% ionic!!
• Electrostatic attraction nondirectional
– no direct anion-cation pair, No ionic molecule
• chemical formula is empirical formula, simply giving the ratio of ions
based on charge balance
• Ions arranged in a pattern called a crystal lattice
• maximizes attractions between + and - ions

14
 Covalent Bonds
• Typical of molecular substances
• Atoms bond together to form molecules
– strong attraction
• Sharing pairs of electrons
• Molecules attracted to each other
weakly
• Often found between nonmetal atoms

15
 Bond Polarity
• Covalent bonding between unlike atoms
results in unequal sharing of the
electrons
– One end of the bond has larger electron
density than the other
• The result is bond polarity
– The end with the larger electron density
gets a partial negative charge
– The end that is electron deficient gets a
partial positive charge
 H •• F 
16
 Electronegativity
• Measure of the ability of an atom to attract shared
electrons
– Larger electronegativity means atom attracts more strongly
– Values 0.7 to 4.0
• Increases across period (left to right) on Periodic Table
• Decreases down group (top to bottom) on Periodic
Table
• Larger difference in electronegativities means more
polar bond
– negative end toward more electronegative atom

17
18
•
Dipole Moment
Bond polarity results in an unequal electron distribution, resulting
in areas of partial positive and partial negative charge
• Any molecule that has a center of positive charge and a center of
negative charge in different points is said to have a dipole
moment
• If a molecule has more than one polar covalent bond, the areas of
partial negative and positive charge for each bond will partially
add to or cancel out each other
• The end result will be a molecule with one center of positive
charge and one center of negative charge
• The dipole moment effects the attractive forces between
molecules and therefore the physical properties of the substance

19
20
The three possible types of bonds: (a) a covalent bond formed
between identical atoms; (b) a polar covalent bond, with both
ionic and covalent components; and
(c) an ionic bond, with no electron sharing.

21
Electron Arrangements And Ion
Charge
• We know
– Group 1A metals form ions with +1 charge
– Group 2A metals form ions with +2 charge
– Group 7A nonmetals form ions with -1
charge
– Group 6A nonmetals form ions with -2
charge
– Group 8A nonmetals do not form ions, in
fact they are extremely unreactive
22
 Electron Arrangements and Ion Charge
• Representative Metals form
cations by losing enough Atom Atoms Ion Ions
electrons to get the same Electron Electron
electron configuration as the Config Config
previous noble gas Na [Ne]3s1 Na+1 [Ne]
• Nonmetals form anions by
gaining enough electrons to Mg [Ne]3s2 Mg+2 [Ne]
get the same electron Al [Ne]3s23p1 Al+3 [Ne]
configuration as the next
noble gas O [He]2s22p4 O-2 [Ne]
F [He]2s22p5 F-1 [Ne]

23
 Electron Arrangements and Ionic Bonding

• Representative metals lose their valence electrons to form

cations
• Nonmetals gain electrons so their valence shell has the
same electron arrangement as the next noble gas
• There have to be enough electrons from the metals atoms
to supply the needed electrons for the nonmetal atoms
– Allows us to predict the formulas of ionic compounds
• In Polyatomic ions, the atoms in the ion are connected
with covalent bonds. The ions are attracted to oppositely
charged ions to form an ionic compound

24
 Properties of Ionic
Compounds
• All solids at room temperature
– Melting points greater than 300°C
• Liquid state conducts electricity, solid state does not
– Liquid = molten
• Brittle and Hard
• Often soluble in water, and when dissolved the solution
becomes an electrical conductor
– When ionic compounds containing polyatomic ions dissolve, the
covalent bonds holding the polyatomic ion do not break, the ion
stays together even though it separates from the other ion
– All strong electrolytes

25
 Bonding and Structure of Ionic
Compounds
• Crystal Lattice = geometric pattern determined by the
size and charge of the ions
• Anions larger than cation
– Almost always
– Anions larger than parent atom, Cations smaller than parent atom
• Anions generally considered “hard” spheres packed as
efficiently as possible, with the cations occupying the
“holes” in the packing
• Arrangement results in each cation being surrounded by
as many anions as will fit
– And visa versa
– Maximizes attractions between ions

26
Lewis Symbols of Atoms and Ions
• Also known as electron dot symbols
• Use symbol of element to represent nucleus and inner
electrons
• Use dots around the symbol to represent valence electrons
– put one electron on each side first, then pair
• Elements in the same group have the same Lewis symbol
– Because they have the same number of valence electrons
• Cations have Lewis symbols without valence electrons
• Anions have Lewis symbols with 8 valence electrons

• •• •• •• ••
Li• Be• •B• •C• •N• •O: :F: :Ne:
• • • • • • ••
•• •• -1
Li• Li+1 :F: [:F:]
• •• 27
 Writing Lewis Structures of
Molecules
• Count the total number of valence electrons from all the
atoms
• Attach the atoms together with one pair of electrons
– A line is often used as shorthand for a pair of electrons that attach
atoms together
• Arrange the remaining electrons in pairs so that all hydrogen
atoms have 2 electrons (1 bond) and other atoms have 8
electrons (combination of bonding and nonbonding)
• Occasionally atoms may violate this rule
– Nonbonding pairs of electrons are also know as Lone Pairs

28
 Covalent Bonds
• Single Covalent Bond the atoms share 2 electrons,
– (1 pair)
• Double Covalent Bond the atoms share 4 electrons,
– (2 pairs)
• Triple Covalent Bond the atoms share 6 electrons,
– (3 pairs)
• Bond Strength = Triple > Double > Single
– For bonds between same atoms, CN > C=N > C—N
– Though Double not 2x the strength of Single and Triple not 3x the
strength of Single
• Bond Length = Single > Double > Triple
– For bonds between same atoms, C—N > C=N > CN

29
 Problems with Lewis
Structures
• Some atoms do not tend to follow the octet rule
– B and Be often found octet deficient
– Elements in the 3rd Period or below often have expanded octets
• Some molecules have an odd number of electrons
• Impossible to accurately draw Lewis structure of molecules
that exhibit resonance
• Sometimes the Lewis Structure does not accurately
describe a structure that explains all the observed
properties of the molecule
• The paramagnetic behavior of O2

30
 Some Geometric Figures
• Linear 180°
– 2 atoms on opposite sides of central atom
– 180° bond angles
• Trigonal Planar
– 3 atoms form a triangle around the central
atom
– Planar 120°
– 120° bond angles
• Tetrahedral
– 4 surrounding atoms form a tetrahedron
around the central atom
– 109.5° bond angles 109.5°

31
2.3. VALENCE BOND THEORY

2.3.1. Investigating the formation of H2 molecule from

two atoms H
 Heitler and London used the quantum mechanics
theory to determine bond energy for a H2 molecule
 What happens to two H atoms as they move toward
each other and form a bond ?
 Investigate the changes in potential energy of two H
atoms with changes in their distance of separation
Figure 3.1. Change in potential energy of two H atoms with changes
in their distance of separation
 When two atoms are far apart, there is no
interaction and the potential energy of this system
is zero
 As two atoms approach each other, the potential
energy of the system decreases (becomes
negative). This trend continues until the potential
energy reaches a minimum value. At this point, it
is most stable
From these results, it is concluded that:
 The chemical bond H-H was formed when two e of
two H atoms have the opposite ms. At the same time, the
overlap of two 1s orbitals of the atoms were occured, the
electron cloud in the internuclear space increases,
resulted in the attraction of two nuclei to form the
chemical bond
If two e have the same spin, the electron cloud in the
internuclear space decreases, but the electron clouds
outside the nuclei increases and these clouds repel each
other and this resulted in separating two nuclei. The
chemical bond was not formed.
Therefore, a H2 molecule was formed due to the pairing
of two electrons with the opposite spin quantum
numbers.
Pauling developed and extended the above results into the
valence bond theory
2.3.2. The basic ideas of the valence bond (VB) theory
Each covalent bond is formed as a result of pairing of
two unpair electrons with the opposite spins from two
reacting atoms. At that time, the overlap of two atomic
orbitals of the reacting atoms are occured to produce the
bonding.
The stronger the overlap of the atomic orbitals, the more
stable the bonding (the smaller the gap in energy for
overlapping orbitals)
Covalent bonds have some features such as direction,
saturation and polarity.
Ex (do at home): Using VB theory, describe
the formation of valent bonding in these
mocules: O2, N2, H2S
2.3.3. Determine valence of an element
According to VB, valence of a given element is
equal to the number of unpaired electrons.
As a result, we can explain monovalence of H,
trivalence of N and bivalence and tetravalent of C
Examples:
H: 1s1 has one unpair electron 1e
 H has monovalence
N: 1s22s22p3

1s2 2s2 2p3

N has three unpair electrons and has trivalence

C: 1s22s22p2
1s2 2s2 2p2

C has two unpair electrons in its ground state, has

bivalence
But in its excited state, the number of unpair electrons
increases due to the shift of the 2s electron to the 2p
subshell.
C*:

As a result, C has four unpair electrons, so has

tetravalence
Note:
• The movement of one paired electron from one orbital
into another empty orbital is only valid for the same shell
or subshell. (ns →np, nd or np → nd, nf)
• The amount of energy requires to transfer a certain atom
from its ground state into the excited state will be
compensated by the energy released during formation of
the bonds.
• Determinating valence of an atom according to VB is true
for the representative elements (A groups)
• These examples were shown that the number of covalent
bonds of an element is limited, so covalent bonds have
saturation property.
2.3.4. The donor- acceptor bond
The donor- acceptor bond is also a covalent bond.
The bond is formed due to the interaction of two
particles: one of which has a pair of electrons A
and the other has an unoccupied orbital B.
A: + B = A- B
The particle that donates the pair of electrons for
the bond is called the donor and the particle with an
unoccupied orbital that accepts the pair is called the
acceptor.
For example:
N (Z= 7): 1s22s22p3 has three unpair electrons.
Three unpair electrons of the N atom will pair with three
unpair electrons of three H atoms to form three N-H
covalent bonds.
However the N atom still has an unshared electron pair,
which can bond with an empty orbital of another H atom to
form one more N-H bond. The 4th N-H bond oriented from
the donor atom to the acceptor.
+
H H

H N: + H H N H

H H

Experimentally showed that the donor-acceptor N-H is

similar to the other N-H (bond length, energy bond).
2.3.5. Direction of a covalent bond
Since atomic orbitals are different in shape, they may
mutually overlap in different ways. Depending on
overlapping and symmetry of the combinating orbitals
(clouds) we can distinguished σ and π bonds.
Sigma (σ) bonds are formed when the overlapping of the
atomic orbitals of two reacting atoms oriented along the
line of connecting two nuclei
Pi (π) bonds are formed when the overlapping of the
atomic orbitals of two reacting atoms located on both sides
of the line connecting two nuclei
Some types of overlapping

s-s overlapping s-p overlapping

p-p overlapping

p-p overlapping

Figure 3.2. Diagram of the overlapping of orbitals in the

formation of sigma and pi bonds
 In molecules, direction of covalent bonds coincides with
the maximum overlapping of the atomic orbitals (clouds).
 This is a direction of covalent bonds, by which we can
determine the geometry of molecules
Example: For H2S
H: 1s1

S: 1s22s22p63s23p4
The S atom has two unpair electrons in 3p subshell
The H atom has one unpair electron.
These two unpair electrons of S will pair with two unpair
electrons of two H atoms to form two covalent bonds H-S
 However, two 3p orbitals of S are perpendicular to each
other in the atom.
To reach the maximum overlapping, the interacting
orbitals of H and S have to orient along the line connecting
two atom centers.
The shape of the overlapping determine the geometry of
the molecular.
 Angular shape
HSH = 92o

1sH +

3py +

1sH

3pz

Figure 3.3. The formation of H2S molecule

3.3.6. The Lewis formulas
In Lewis formulas, each covalent bond represents by a dash,
each donor-acceptor bond- by an arrow and each unshared
electron pair of a central atom represents by two dots.
Examples:
* Molecule H2S has two covalent bonds and the S atom has two
unshared electron pairs. The Lewis formula for H2S as follows:
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
2.4.1. Hybridization of atomic orbitals
Hybridization is a mixing of atomic orbitals in an
atom (usually a central atom) to generate a set of
hybrid orbitals.
The hybrid orbitals overlap with atomic orbitals of
another atoms to produce more stable covalent bonds.
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
2.4.2. The types of hybridization and geometric shape
sp hybridization:
 When one ns orbital combines with one np orbital to form
two equivalent sp hybrid orbitals.
 These two hybrid orbitals oriente on the same line, so that
the angle between them is 180o
1AOs + 1AOp  two hybrid sp orbitals
p Hybridization
+ - - +

sp
 sp hybridization occurs at AB2 molecules with no lone
pairs on the central atom such as BeF2, BeCl2, BeI2 having
linear molecular geometry.
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
Example: BeCl2
 2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
sp2 hybridization:
One ns orbital hybridizes with two np orbitals to form
three equivalent sp2 orbitals.
These three hybrid orbitals point towards the corners of
an equilateral triangle.
1AOs + 2AOp  three hybrid sp2 orbitals
pz
+
120o

- -
py
+ - +

sp2 hybridization occurs at AB3 molecules and ions with no unshared

electron pairs on the central atom have trigonal planar geometry. (For
examples: BF3, BCl3)
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
Example: BF3

Planar
triangle
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
sp3 hybridization:
One ns orbital hybridizes with three np orbitals to form
four equivalent sp3 orbitals.
These four hybrid orbitals are directed towards the four
corners of a regular tetrahedron, which has a 109.5o angle
from any corner to the center to any other corner (bond
angle of 109.5o)
1AOs + 3AOp  four hybrid sp3 orbitals
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES

+ + +

The shape and orientation of sp3 hybrid orbitals

sp3 hybridization occurs at AB4 molecules and ions with no

unshared pairs on the central atom have a regular tetrahedral
geometry (CH4, NH4+)
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
Example: CH4
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
Example: CH4
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES

Tetrahedral, bond angle = 109.5o

2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
2.4.3. Influence of lone pair of electrons at a central atom
on molecular geometry
For AB3E molecule: NH3, NF3

lone pair repels bonding pair

Due to the lp/bp repulsion in NH3, its

bond angle is less than the angle of
109.5o
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
For AB2E2: H2O, H2S

The repulsion of lp/lp in H2O is much greater than that

of lp/bp in NH3, therefore the decrease in the H-O-H
bond angle in H2O (from 109.5o to 104.5o) is greater than
that in the H-N-H bond angle in NH3
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
2.4.3. Predict hybridization of a central atom and molecular
geometry
Based on a total of the number of sigma bonds and
unshared electron pairs it can be predicted the hybridization
type of a central atom.
According to the hybridization type and the number of
bonded atoms with the central atom we can determine the
geometry of molecule.
+ If the total is equal to 2, a central atom has sp
hybridization
+ If the total is equal to 3, a central atom has sp2
hybridization
+ If the total is equal to 4, a central atom has sp3
hybridization
 2.4.3. Predict hybridization of a central atom
and molecular geometry (VSERP rule)
• Step 1: write Lewis structure of molecule
Ex: NH3

• Step 2: Change Lewis structure to AXmEn

A: central atom
X: around of A atom
m: the numbers of X atom
E: pair of nonbonding electron of A
n: The numbers of E
2.4.3. Predict hybridization of a central atom
and molecular geometry (VSERP rule)

• Considering (m+n)
 2.4.3. Predict hybridization of a central atom
and molecular geometry (VSERP rule)
Total A Geometry of molecule Example Bond angle
hybridiz
(m+n)
ation
m = 4, Tetrahedral CH4, CCl4, =109,5o
n=0 …
4 sp 3
m = 3, Trigonal NH3, <109,5o
n = 1 pyramid H3O+…..
m = 2, Angular (V- H2O, …. <109,5o
n = 2 shape)
m = 3, Trigonal planar BF3, SO3…. =120o
n=0
3 sp2
m = 2, Angular SO2,…. <120o
n=1
2 sp Linear CO2, = 180o
BeCl2….
5 sp3d
6 sp3d2
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
For examples:
H2O: has two sigma bonds and two lone pairs of
electrons. The O atom of H2O has sp3 hybridization
H2O has angular geometry
NH3 has three sigma bonds and one lone pair of
electrons. The N atom of NH3 has sp3 hybridization
NH3 has trigonal pyramid
CH4 has four sigma bonds and has no pair of electrons.
The C atom of CH4 has sp3 hybridization and
tetrahedron geometry.
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
Note:
The effect of hybridization at central atoms in the
second period: Be, B, C, N, O
* Be: sp, 180o , linear shape
* B: sp2, 120o or sp3 109o8’
+ BF3: sp2, no lone pair of electrons, 120o and trigonal
planar
+ BF4- sp3, 109o8’, no lone pair of electrons and
tetrahedron
* C: sp3, 109o8’ or sp, 180o
+ CH4: sp3, no lone pair of electrons, tetrahedron
2.4. HYBRIDIZATION OF ATOMIC ORBITALS
AND GEOMETRIC SHAPE OF MOLECULES
* N: sp3
+ NH3: sp3, one lone pair of electrons, 107o3’, trigonal
pyramid
+ NH4+: sp3, no lone pair of electrons, 109o8’,
tetrahedron
* O: sp3
+ H2O: sp3, two lone pair of electrons, angular
geometry, 104o5’
+ H3O+: sp3, one lone pair of electrons, trigonal
pyramid, 107o3’
Conclusion: the effect of hybridization at central atoms
decreases from lef to right
2.5. MOLECULAR ORBITAL THEORY
Using the concept of hybridization (for
hybridization method and VB method), molecular
geometries can be explained.
In many cases, VB theory cannot satisfactorily
account for observed properties of molecules
Example 1: Consider the oxygen molecule, its Lewis
structure is
O O
+ All the electrons in O2 are paired and the molecule
should therefore be diamagnetic.
+ But experiments have shown that O2 is paramagnetic
with two unpaired electrons
2.5. MOLECULAR ORBITAL THEORY
Example 2:
+ According to VB method, we cannot explain the
bonding in H2+ (bond order of 0.5)
+ or other species such as O2+, NO+, O22-
These questions can only be answered by another
method
2.5. MOLECULAR ORBITAL THEORY
Magnetic and other properties of molecules can
be explained by another approach called molecular
orbital theory (MO).
Molecular orbital theory describes covalent bonds
in terms of molecular orbitals. Molecular orbitals
(MO) result from interaction of the atomic orbitals
of the bonding atoms and are associated with the
entire molecule.
The difference between a molecular orbital (MO)
and atomic orbital (AO) is that an atomic orbital is
associated with only one atom.
2.5. MOLECULAR ORBITAL THEORY
2.5.1. Investigating the formation of H2 - Bonding-
antibonding molecular orbitals
According to MO theory, the overlap of two 1s
orbitals of two H atoms leads to the formation of two
molecular orbitals: One bonding molecular orbital
(MO) and one antibonding molecular orbital (MO*).
A bonding molecular orbital has lower energy and
greater stability than the atomic orbitals from which it
was formed.
An antibonding molecular orbital has greater energy
and lower stability than the atomic orbitals from which
it was formed.
2.5. MOLECULAR ORBITAL THEORY
In the bonding molecular orbital the electron
density is greater between the nuclei of the bonding
atoms.
In the antibonding molecular orbital, on the other
hand, the electron density decreases to zero
between the nuclei.
Two electrons occupy the bonding molecular
orbital, which leads to sigma bond.
2.5. MOLECULAR ORBITAL THEORY

Figure 2.7. Molecular orbital diagram for the combination of the

two 1s orbitals from two H atoms to form to MOs
2.5. MOLECULAR ORBITAL THEORY
Note:
Although, we have used the H2 molecule to
illustrate molecular orbital formation, but the
concept is equally applicable to other molecules.
In the H2 molecule we consider only the
interaction between 1s orbitals; with more complex
molecules we need to consider additional atomic
orbitals as well.
2.5. MOLECULAR ORBITAL THEORY
2.5.2. Molecular orbital configurations
- Only covalent AO of bonding atom interaction
to formation MO
- Covalent electrons of bonding atoms form
electrons of molecule
Example: In O2, each O atom has 6 covalent
electrons, so, there are 12 electrons in O2
- The number of MO = the number of interation
AO
2.5. MOLECULAR ORBITAL THEORY
2.5.2. Molecular orbital configurations
2.5.2.1. The required conditions for combinating
atomic orbitals
 The combinating atomic orbitals possess the
approximate energy
 The combinating atomic orbitals have to overlap
clearly, therefore, consider only the combinating of
the outermost atomic orbitals
 The combinating atomic orbitals have the same
symmetry with the line connecting two nuclei.
2.5. MOLECULAR ORBITAL THEORY
2.5.2.2. Types of molecular orbitals (MOs)
Based on the symmetry of the overlap of two atomic
orbitals, we can distinguish sigma and pi MO:
MO- was produced, when the overlap is
concentrated symmetrically around a line between
the two nuclei of the bonding atoms:
ns(1) + ns(2)  s and s*
npx(1) + npx(2)  x and x*
2.5. MOLECULAR ORBITAL THEORY

The overlap of two ns orbitals of two atoms to form

MO-σ and MO- σ*
2.5. MOLECULAR ORBITAL THEORY

The overlap of two npx orbitals of two atoms to form

MO-σ and MO- σ*
2.5. MOLECULAR ORBITAL THEORY
MO-  was produced when the overlap is
concentrated above and below a line connecting
two nuclei of the bonding atoms.
npz(1) + npz(2)  z and z*
npy(1) + npy(2)  y and y*
2.5. MOLECULAR ORBITAL THEORY

Figure.2.9. Production of y and y* MOs by overlap of

two 2py (orbitals from two atoms)
2.5. MOLECULAR ORBITAL THEORY
2.5.2.3. Molecular orbital energy level diagram
The order energy of molecular orbitals must be
consistent with two principles:
The lower energy the combinating atomic orbitals
have, the lower energy level the molecular orbitals
can be obtained.
The stronger the overlapping of two atomic
orbitals, the bigger the difference of the bonding
MO and antibonding MO.
Arrange molecular orbitals from low to high
energy levels.
2.5. MOLECULAR ORBITAL THEORY
2.5.2.4. Arranging valence electrons of a molecule to
MOs according to the following rules:
The Pauli exclusion principle: Like an atomic
orbital, each molecular orbital can accommodate
up to two electrons with opposite spins
The building up principle (the stable principle):
Place electrons first in the lower-energy bonding
molecular orbitals.
Hund’s rule: When electrons are added into
molecular orbitals of the same energy, the most
stable arrangement is that electrons enter these
MOs with parallel spins
2.5. MOLECULAR ORBITAL THEORY
2.5.2.5. Determining the basic characteristics of a molecule

The bond order: N N*


2

Where N is the number of electrons in bonding MOs

and N* is the number of electrons in antibonding MOs

The bond order indicates the strength of a bond. The

greater the bond order, the more stable the bond, the
shorter the bond length.
2.5. MOLECULAR ORBITAL THEORY
Note:
- The bond order can be a fraction or a bond order
of zero means that the molecule cannot exist.
- Determining magnetism of a molecule:
If a molecule has unpair electrons, it should be
paramagnetic; if a molecule has no unpair
electrons, it should be diamagnetic.
2.5. MOLECULAR ORBITAL THEORY
2.5.2.6. Investigating homonuclear molecules (A2) of
second-period elements
* Define the MOs
The second-period elements has four valence
atomic orbitals: 2s, 2px, 2py and 2pz. The identical
orbitals will overlap each other as follows:
2s + 2s  s and s*
2px + 2px  x and x*
2pz + 2pz   z and  z*
2py + 2py  y and y*
 2.5. MOLECULAR ORBITAL THEORY
Molecular orbital energy level diagram

The electron configuration: (KK) 2s 2s* 2pz=2py 2px

2pz*=2py*2px*
from Li to N
 2.5. MOLECULAR ORBITAL THEORY

The electron configuration: (KK) 2s 2s* 2px 2pz=2py

2pz*=2py*2px* from O2 to Ne2
Example: Write molecule configuration and characteristic
molecule (bond order and magnetic property): N2, O2

• N2 (7N: [Ne]2s22p3) → N2 has 10e

(KK) 2s2 2s*2 2pz2=2py2 2px2
P=(N-N*)/2=(8-2)/2=3
N2 is diamagnetic because of having no
unpaired electron
• O2 (8O: [Ne]2s22p4) → O2 has 12e
(KK) 2s2 2s*2 2px2 2pz2=2py2 2pz*1=2py*1
P=(N-N*)/2=(8-4)/2=2
O2 is paramagnetic
2.5. MOLECULAR ORBITAL THEORY
The inversion of the 2px orbital and the 2pz 2py
orbitals can explain that:
* for the elements at the beginning of the period the
difference in energy of 2s and 2p atomic orbitals is low,
as a result the electron in 2px orbital will experience
greater repulsion from the electrons in 2s
* the repulsion between the electrons in 2px and 2s
decreases from left to right in the second period,
therefore the 2px orbital is higher in energy than the
2px and 2py orbitals only for Li2 to N2, but is lower in
energy than the 2px and 2py orbitals for elements from
O2 to Ne2.
2.5. MOLECULAR ORBITAL THEORY
2.5.2.7. Heteronuclear diatomic molecules of
second-period elements (AB)- χB > χA
 Select atomic orbitals for combinating to form MOs as in
the case for homonuclear molecules (A2)
(2s)A + (2s)B  s and s*
(2px)A + (2px)B  x and x*
(2pz)A + (2pz)B   z and  z*
(2py)A + (2py)A  y and y*
The energy oder and energy diagram of AB
molecule is similar to A2 (A: Li-N) (The lower χ , the
higher AO energy in energy diagram)
2.5. MOLECULAR ORBITAL THEORY
 MOs energy level diagram, note that:
+ If χB > χA, the atomic orbitals of B are in lower
in energy than the corresponding orbitals of A.
+ Accordingly, the bonding MOs are closed to the
energy level of the atomic orbitals of B
+ While the antibonding MOs are closed to the
energy level of the atomic orbitals of A
Fill electrons with the MO by increasing in energy
Determine characteristics of molecules
2.5. MOLECULAR ORBITAL THEORY
Example: Write electron configuration and MO
energy level diagram of NO
• χ O > χN
• Combinating atomic orbitals of two atoms
• Diagram of energy level of MOs
• Arrange electron into the MOs from the lowest to
the highest
2.5. MOLECULAR ORBITAL THEORY
2.5. MOLECULAR ORBITAL THEORY
The energy of the bonding MOs in NO is closer to
the energy of the atomic orbitals of O and these
MOs in NO have more oxygen - like atomic orbital
character.
The energy of the antibonding MOs in NO is
closer to energy of the atomic orbitals of N and the
antibonding MOs have more nitrogen like atomic
orbital character.
2.5. MOLECULAR ORBITAL THEORY
The differences ΔE1, ΔE2, ΔE3 depends on the
difference in (EN) between two atoms.
The greater the energy differences, the more
polar is the bond.
 On the other hand, the energy differences reflect
the degree overlap between atomic orbitals. The
smaler the differences, the more the atomic orbitals
can overlap, the greater is the covalent bond
2.5. MOLECULAR ORBITAL THEORY
 Chapter 3: Collecting elements state
3.1. Molecular structure
3.1.1. Polar and nonpolar molecules
Nonpolar molecule is a molecule which has
a symmetrical structure, so the centre of
negative charges coincides with the center of
positive charges
* such as homonuclear diatomic molecules
must be nonpolar, or molecules have
symmetrical structure like CH4, NH4+, CO2,
BF3,...
3.2. Molecular structure

Polar molecule is a molecule which has

asymmetrical structure, therefore the centre of the
negative charges does not coincide with the centre
of the positive charges
* such as heteronuclear diatomic molecules, or
molecules have lone pair of electrons like NH3, H2O,
…
3.1. Molecular structure
3.1.2. Dipole moment
Each polar molecule seems to be an electric dipole
consisting of two opposite charges, separating at a
distance of d.
q q

+ -

Dipole moment is given to evaluate the polarity of a

molecule. The dipole moment , defined as the
product of the distance d between two charges of
equal magnitude and opposite sign and magnitude
of the charge q.
3.1. Molecular structure
  q .d
[C.m] or [D] (debyes), 1D= 0.333x10-30 C.m

The bigger the dipole moment, the more polar the

molecule.
+ The covalent compounds (that contain covalent
bonds) have the dipole moment ranging from 0 to 4D.
+ The ionic compounds have the dipole moment in the
range of 4-11D.
Dipole moment is a vectorial magnitude, directing from
an atom with lower EN to an atom with higher EN.
3.2. Molecular structure
Example:
Hydrogen fluoride HF.
The H-F bond is polar covalent in which the
shared electron pair will be attracted towards the
F atom (with higher electronegativity), thus the
opposite charges will be formed: +δ and –δ.

δ- over the F atom indicates a “partial negative charge” . This

mean that the F end of the molecule is somewhat more
negative than the H end. δ+ over the H atom indicates a
“partial positive charge” or the H end of the molecule is
positive with respect to the F end.
 Chapter 3: Collecting elements state
3.1.3. The factors influence on dipole moment of
molecules
1. Dipole moment of molecules depends on the
difference in electronegativities (EN) of the bonding
atoms.
The larger the difference in EN of the bonding
atoms the higher the dipole moment of the
molecule.
 Chapter 3: Collecting elements state
Example:
 Chapter 3: Collecting elements state
2. The asymmetry of molecules:
CO2, BF3 NH4+, is symmetrical, so its dipole
moment = 0
NH3 or H2O have lone pairs of electrons (one lone
pair for NH3 and two pairs for water), so their dipole
moments must not be equal to zero.
μNH3 = 1.46D, μH2O = 1.84D
3. The influence of unshared electron pairs:
*NH3 and NF3 has the same structure- trigonal
pyramid, thus their polarity should have the same
value, but in fact μNH3 = 1.46D and μNF3 = 0.2D
Chapter 3: Collecting elements state
 Chapter 3: Collecting elements state
3.2. WEAK BONDS
Besides chemical bonds such as covalent and ionic
bonds having the energies of about several hundreds
KJ.mol-1, there are a few types of weak bonds with
much smaller energies, like hydrogen bond and Van
der Waal’s forces
The weak bonds play an important role in phase
transfers such as evaporation, melting, sublimation
and etc.
Chapter 3: Collecting elements state
3.3.1. Hydrogen bond:
The hydrogen bond is a special type of interaction
between the hydrogen atom in a polar bond, such as
N-H, O-H or F-H and an electronegative O, N or F
of other molecule. This interaction is written:
A-H......B or A-H ....A
A and B represent O, N, or F; A-H is one molecule
or part of a molecule and B is a part of another
molecule
For example:
H+ - F- …. H+ - F-
Chapter 3: Collecting elements state
For example:
H+ - F- …. H+ - F-
The formation of hydrogen bond as follows:
+ In molecule HF, the bp attract towards F, the H
atom will become positive due to having only
nuclear, therefore the H can again bond with
another F of other molecule by hydrogen bond
The average energy of a hydrogen bond is in the
range of 8-40 KJ.mol-1.
The hydrogen bonds have a powerful effect on the
structures and propeties of many compounds
Chapter 3: Collecting elements state
Due to its small energy, the hydrogen bond
influences only on physical properties of substances
such as boiling temperature, melting temperature
or dissolubility.
Examples:
Hydrogen bonds lead to conjugation of molecules:
(HF)n, n =2-6; (H2O)n, n= 2-4.
Chapter 3: Collecting elements state
Chapter 3: Collecting elements state
Due to H bonds
It becomes more difficult to evaporate or boil for
molecules, thus evaporation temperature, boiling
temperature increase.
HF has much higher boiling, melting temp. as
compared to another compounds in the same
series of HCl, HBr, HI
HF HCl HBr HI
tboil, oC 19,5 -84,9 -66,7 -35,8
Tmelt., oC -83 -114,2 -88 -50,8
Chapter 3: Collecting elements state
 Hydrogen bonds lead to decreasing in electronic
dissociation of substances.
HF is a weak acid and weakly electronic dissociation
substance, while another substances in the series, such as
HCl, HBr, HI are strong acid and strongly electronic
dissociation substances
Hydrogen bond leads to an unusual phenomena of
water density.
In general, by increasing temp., the densities of
substances decrease, however, for water, when t< 4oC,
the density of water increases by increasing temp. and
reaches maximum at 4oC and afterwards its density
decreases by increasing temperature.