Chapter 2

Molecular structure – chemical bond

ATOMs ? Molecule
s
Chemical
bonds
- Covalent bonds
- Ionic bonds
- Other bonds (metallic, hydrogen, Van der Walls)
2.1. Basic Concepts
1. Bond energy (Eb, kj/mol or kcal/mol): is the average value of the
gas-phase bond dissociation energies.
Eb is the measure of bond strength in a chemical bond.
Eb ↑ → bond strength ↑

2. Bond length (db): is the average distance between nuclei of

two bonded atoms in a molecule

db ↑ → stability ↓

3. Bond Angles:
2.1. Basic Concepts
4. Bond Order (B.O): is the number of chemical bonds between a pair
of atoms

B.O = 1 B.O = 2 B.O = 3

B.O = 1.5 ?
B.O ↑ → db ↓ → Stability ↑
2.1. Basic Concepts
5. Electronegativity (χ): The ability of an atom in a molecule to attract
shared electrons to itself. Covalent or
ionic bonds

ATOMs Molecules
s
Ionic bonds (Metal-
nonmetal):
Δχ > 1.7

Covalent bonds
(nonmetal-nonmetal):
0≤ Δχ ≤1.7
Δχ = 0: nonpolar
Δχ > 0: polar
2.1. Basic Concepts
6. Covalent molecules including nonpolar and polar molecules.

 A polar molecule is electrically asymmetrical, resulting in charges

at two points. The molecule is said to have a molecular dipole
(lưỡng cực) or dipole moment.

O O C O
H Cl O
H H C
H3C CH3

 NOT all molecules that contain polar bonds will be polar molecules!
2.2. Covalent Bond

Two main Theories for forming Covalent

Bond:

1. Valence Bond (VB)

2. Molecular Orbital (MO)
1. Valence Bond (VB) theory
The basic idea
 Two half-filled orbitals overlap to form a covalent bond.
 The electrons in this new
probability density are then
shared by both atoms (equally
attracted to both nuclei).
Arrange themselves to have maximum overlap of
their half filled orbitals, producing a bonding orbital of
lowest energy
Types of Covalent Bonds

Orbitals can overlap in two main

ways creating two different types
of covalent bonds
Sigma bonds (σ)
Pi bonds (π)
The σ Bonds
 The σ bonds are formed from overlapping of AO
according to bond axis

 The σ bonds are the strongest type of covalent

chemical bond
The π Bonds
 The π bonds are required two lobes (thùy) of one
involved AO overlapping two lobes of the other AO

 The π bonds are usually weaker than σ bonds

Formation of Covalent Bonds
 Octet rule: Chemical compounds tend to form that each atom, by
gaining, losing, or sharing electrons, has an octet of electrons (or
doublet in Hydrogen case).

F-F

H : Cl

Lewis structure
Comments on Octet Rule

 2nd period elements C, N, O, F observe the octet rule. However, 2nd

row elements B and Be often have fewer than 8 electrons around
themselves → they are very reactive.

 3rd period and heavier elements CAN exceed the octet rule using
empty valence d orbitals.

Ex. Clo (Z= 17) explain why Clo possesses various oxidation
numbers: Cl-, Cl+, Cl+3, Cl+5, Cl+7
Lewis Structures

 Shows how valence electrons are arranged among atoms in a

molecule.

 Reflects central idea that stability of a compound relates to noble

gas electron configuration.
Lewis Structures
Completing a Lewis Structure -CH3Cl
Make carbon the central atom
Add up available valence electrons: C = 4, H =
(3)(1), Cl = 7 Total = 14

Complete octets on
atoms other than H
hydrogen with remaining .
..
electrons
H C Cl

..
.
. ..

H
Types of Bonds
 Single bond = 1 σ bond

 Double bond = 1 σ + 1 π bond

Two pairs of shared electrons

 Triple bond = 1 σ + 2 π bonds

Three pairs of
shared electrons
Types of Bonds
 Resonance
Occurs when more than one valid Lewis structure can be
written for a particular molecule.

These are resonance structures. The actual structure is an

average of the resonance structures.

Neither structure is correct.

Question?
Lets look at a molecule of
methane, CH4.

What is the expected orbital notation of carbon

in its ground state?

C (Z = 6): 1s22s22p2

Can you see a problem with this?

How to form bonds of carbon according to octet rule?
Promotion & Hybridization (kích thích & lai hóa)
 Certain atoms can change their electron configuration to bond
and form a wide variety of compounds. → two steps:
Promotion of an electron to a higher energy orbital &
hybridization or blending of orbitals creating a new type of
orbital for bonding
Most of the time atoms exist in their “ground state” but, in
certain cases the instant before bonding promotion takes
place allowing more bonding spaces:

Promotion
Hybridization (Lai hóa)
 Hybridization is the combining of two or more orbitals of
nearly equal energy within the same atom into orbitals of
equal energy.

 No orbitals are “lost” due to merging – if we blend one s

orbital and one p orbital, we will end up with TWO hybrid
orbitals!

Covalent bonds are formed by:

Overlap of hybrid orbitals with atomic orbitals
Overlap of hybrid orbitals with other hybrid orbitals
Types & Names of hybrid orbitals
 The type of hybrid orbital depends upon the orbitals which
have been blended
 sp3
 sp2
 sp
 Others (sp3d, sp3d2,…)
sp3 hybrid Orbitals (CH4)
 In the case of CH4, they call the
hybridization sp3, meaning that an
s orbital is combined with three p
orbitals to create four equal hybrid
orbitals.
 These new orbitals have slightly
MORE energy than the 2s orbital.
and slightly LESS energy than the
2p orbitals.

Bond angle is 109o28

sp2 hybrid Orbitals (C2H4, BF3,…)

 The sp2 combines two orbitals from a p sublevel with one

orbital from an s sublevel.

Bond angle is 120o

 Notice that one p orbital remains unchanged.

sp hybrid Orbitals (C2H2, BeCl2,…)

 The sp hybridization includes one s orbital combining

with a single p orbital.

Bond angle is 180o

 Notice that this produces two hybrid orbitals, while

leaving two normal p orbitals
Hybridization Involving d Orbitals

promote

3s 3p 3d 3s 3p 3d
unhybridized P atom vacant d orbitals
P = [Ne]3s23p3 hybridize

Ba
F
F Be five sp3d orbitals 3d
P F Be

F
Be degenerate
F orbitals

Ba (all EQUAL)

Trigonal bipyramidal
Summary
Question?
 VB theory fails to explain the bonding in many simple molecules.

Example: How to explain the paramagnetism of oxygen (containing

unpaired electrons)?

: :
: :
O=O
Resonance is another example of the limitations of valence bond
theory. Bond lengths and strengths are intermediate between
single, double or triple bonds.
2. Molecular Orbital (MO) theory
 Molecular orbitals result from the combination of atomic
orbitals (AO)
 Molecular orbitals form when atomic orbitals with similar
energies and proper symmetry can overlap.

 Since orbitals are wave functions, they can combine either

constructively (forming a bonding molecular orbital), or
destructively (forming an antibonding molecular orbital).
 Name of MO is similar to AO (σ, π,..)

Example: Forming H2 molecule from 2 H atoms

σ*1s
↑ ↑
1s ↑↓ 1s
HA H2 σ1s HB
Bonding and anti-bonding MO
Constructively:
Ψ(σ) or Ψ+ = (1/√2 ) [φ(1sa) + φ(1sb) ]
Destructively:
Ψ(σ*) or Ψ- = (1/√2 ) [φ(1sa) - φ(1sb) ]

The bonding MO increased The anti-bonding MO

electron density and lower decreased electron density
energy. and greater energy.
Bonding and anti-bonding MO
Energy
This orbital is called the
Lowest Unoccupied
s* Molecular Orbital (LUMO)

1s This orbital is called the

s Highest Occupied Molecular
Orbital (HOMO)

ELUMO > EHOMO

Explaining Properties of molecule
Magnetism

Paramagnetism (thuận từ): Having unpaired electrons

Diamagnetism (Nghịch từ): Having NO unpaired electrons

Bonding Order (B.O)

B.O =

B.O = 0 the molecule is inexistent!

MO diagrams
1. X2 molecules in row 1

X X2 X
s s*
Energy
1s 1s
ss

→ Describing MO diagrams: H2, H2+, H2- and He2?

→ Configura on, B.O and Magne sm as well?
MO diagrams
2. X2 molecules in row 2: Describing MO diagrams: Li2 (Z = 3),
Be2 (Z=4), B2 (Z=5), C2 (Z = 6), N2 (Z=7), O2 (Z=8), F2(Z=9),
Ne2(Z=10)? → Configura on, B.O and Magne sm as well?

Forming MOs for final elements

O2, F2 and Ne2:
1s combining 1s → σ1s σ1s*
2s combining 2s → σ2s σ2s*
2px combining 2px → σx σx*
2py, 2pz combining 2py, 2pz → πy =πz, πy*= πz*

Configuration of MO: σ21s σ*21sσ22s σ*22sσ2x π2y =π2z π*2y= π*2z σ*2x
MO diagrams
2. X2 molecules in row 2: Describing MO diagrams: Li2 (Z = 3),
Be2 (Z=4), B2 (Z=5), C2 (Z = 6), N2 (Z=7), O2 (Z=8), F2(Z=9),
Ne2(Z=10)? → Configura on, B.O and Magne sm as well?
Forming MOs for Initial elements Li2, Be2, B2, C2
and N2:
1s combining 1s → σ1s σ1s*
σ*
2s,2px combining 2s, 2px → σ2s σ2s*σx σx* x

2py, 2pz combining 2py, 2pz → πy =πz, πy*= πz* π*y π*z

E πy =πz < Eσx

σx
πy πz
Configuration of MO:
σ21s σ*21sσ22s σ*22sπ2y =π2z σ2x π*2y= π*2z σ*2x σ*2s

σ2s
Summary for X2

2s-2pz mixing
MO diagrams
3. AB molecules in row 2: Similar to 5 initial elements

Configuration of MO:
σ21s σ*21sσ22s σ*22sπ2y =π2z σ2x π*2y= π*2z σ*2x

Example: Describing MO of CO

Configuration of AOs:
C: 1s22s22p2
O: 1s22s22p4
χO > χC
Configuration of CO:
σ21s σ*21sσ22s σ*22sπ2y =π2z σ2x
Ionic Bond
 Electrons are transferred

 Electronegativity differences are generally greater than

1.7
 The formation of ionic bonds is always exothermic!
Ionic Bond

Ionic compounds are NOT molecule. They are

called salts or crystal

ALWAYS formed between metals and non-metals

[METALS ]+ [NON-METALS ]-

Lost e-
Gained e-
Metallic Bond
 Occurs between like atoms of a metal in the
free state
 Valence e- are mobile (move freely among all
metal atoms)
 Positive ions in a sea of electrons
Hydrogen Bonding
 Bonding between hydrogen and more electronegative neighboring
atoms such as O, N and F
 Intermolecular (liên pt) bonding: melting
point, boiling point, acidicity, solubility
are high.
 Intramolecular (nội pt) bonding: melting
point, boiling point, solubility are low
Van de Waals bond
 Van der Waals bond are the residual attractive or repulsive
forces between molecules or atomic groups that do not arise
from a covalent bond, or ionic bonds.

 Non-polar molecules can exist in liquid and solid phases

because of van der Waals forces

Example: Exist between CO2, CH4, CCl4, CF4, diatomics and

monoatomics
Van de Waals bond