Molecular structure and bonding

Lewis structures
2.1 The octet rule
2.2 Structure and bond properties
2.3 The VSEPR model
Valence-bond theory
2.4 The hydrogen molecule
2.5 Homonuclear diatomic molecules
2.6 Polyatomic molecules
Molecular orbital theory
2.7 An introduction to the theory
2.8 Homonuclear diatomic molecules
2.9 Heteronuclear diatomic
2.10 Bond properties
 Lewis Theory of Bonding

Octet Rule
All elements except hydrogen ( hydrogen have
a duet of electrons) have octet of electrons
once they from ions and covalent compounds.
Noble gas configuration valence
valence
ee- -
The noble gases are noted for He 22
He
their chemical stability and Ne
Ne 88
existence as monatomic Ar
Ar 88
Kr
Kr 88
molecules. Xe
Xe 88
Except for helium, Rn
Rn 88
They share a common electron configuration
that is very stable.
This configuration has 8 valence-shell electrons.
All other elements reacts to achieve Noble Gas
Electron Configurations.
 The octet rule
• Atoms are most stable if they have a filled or
empty outer layer of electrons.
• Except for H and He, a filled layer contains 8
electrons - an octet.
• Two atoms will
gain or lose (ionic compounds)
share (covalent compounds)
compounds
Many atoms with fewer electrons will
share (metallic compounds)
What changes take place
during this process of achieving
closed shells?
a) sharing leads to covalent bonds and
molecules
b) gain/loss of electrons lead to ionic bond
c) Sharing with many atoms lead to
metallic bonds
Lewis Electron Dot symbols
Basic rules
Draw the atomic symbol.

Treat each side as a box that can

X hold up to two electrons.

Count the electrons in the valence

shell.

Start filling box - don’t make pairs

unless you need to.
 Lewis symbols
Lewis symbols of second period elements

Li Be B C

N O F Ne
What is a Lewis Structure (electron-dot
formula) of a Molecule?

• A molecular formulas with dots around atomic symbols

representing the valence electrons

• All atoms will have eight (octet) of electrons

(duet for H) if the molecule is to be stable.

Single covalent bonds

H
H H H C H F F
H

Do atoms (except H) have octets?

 Lewis structures
• This is a simple system to help keep track of
electrons around atoms, ions and molecules
- invented by G.N. Lewis.
• If you know the number of electrons in the
valence-shell of an atom, writing Lewis
structures is easy.
• Lewis structures are used primarily for s- and
p-block elements.
 How do you get the Lewis Structure from Molecular
formula?
• Determine the central atom
• Create the structure of atoms
• Add all valence electrons and get valence electron pairs
• Put σ bonding between central atom with terminal atoms
• Fill octet to all atoms (duet to hydrogen)
• Calculate electrons remain, then put the electrons remain as
PEB or single electron if the total of amount of electrons are add
• Check the formal charge of every atoms if the minimal charge
didn’t achieve so change PEB to π bonding until minimal formal
charge achieved
Lewis Structure of H2O
 Types of electrons
Bonding pairs
Two electrons that are shared between two
atoms. A covalent bond.
Unshared (nonbonding
( ) pairs
A pair of electrons that are not shared between
two atoms. Lone pairs or nonbonding electrons.

oo Unshared
H Cl pair
oo
oo

oo
Bonding pair
 Lewis Structure of H2O

2 bond pairs= 2 x 2 = 4 2 lone

pairs = 2 x 2 = 4
Total 8 = 4 pairs
Bond pairs: an electron pair shared by two
atom in a bond. E.g. two pairs between O--H
in water.
Lone pair : an electron pair found solely on a
single atom. E.g. two pairs found on the O
atom at the top and the bottom.
Lewis Structure of H2S
Lewis Structure of CCl4
 What is the Lewis Structure?
• CO2

• NH3 (PH3)

• PCl3 (PF3, NCl3)

Lewis structure and multiple
bonds
This arrangement needs
O C O too many electrons.

How about making some double bonds?

O=C=O That works!

= is a double bond,
the same as 4 electrons
 Multiple bonds
So how do we know that multiple bonds really
exist?
The bond energies and lengths differ!
Bond Bond Length Bond energy
type order pm kJ/mol

C C 2 134 615
C C 1 154 347
C C 3 120 812
 Formal Charges
Formal chage = valence electrons - assigned electrons
•There are two possible Lewis structures for a molecule. Each
has the same number of bonds. We can determine which is
better by determining which has the least formal charge. It
takes energy to get a separation of charge in the molecule
•(as indicated by the
• formal charge) so the structure with the least formal charge
should be lower in energy and thereby be the better Lewis
structure
 What is Resonance Structures?

•Several Lewis structures that need to be drawn for

molecules with double bonds

•One Lewis structure alone would not describe the

bond lengths of the real molecule.

•E.g. CO32-, NO3-, NO2-, SO3

 Resonance structures

Sometimes we can have two or more equivalent Lewis

structures for a molecule.

O-S=O O=S-O

They both - satisfy the octet rule

- have the same number of bonds
- have the same types of bonds

Which is right?
Resonance structures of SO2
They both are!

O -S=O O =S- O

O S O
This results in an average of 1.5 bonds
between each S and O.
Resonance structures of CO32- ion
Resonance structures of NO3- ion
Resonance structures of SO3
Resonance structures of NO ion
2
-
Resonance structures of C6H6
• Benzene, C6H6, is another example of a compound
for which resonance structure must be written.
• All of the bonds are the same length.

or
Exceptions to the octet rule
Not all compounds obey the octet rule.
• Three types of exceptions
• Species with more than eight electrons
around an atom.
• Species with fewer than eight electrons
around an atom.
• Species with an odd total number of electrons.
Atoms with more than eight electrons

• Except for species that contain hydrogen, this is

the most common type of exception.

• For elements in the third period and beyond, the

d orbitals can become involved in bonding.
Examples
• 5 electron pairs around P in PF5
• 5 electron pairs around S in SF4
• 6 electron pairs around S in SF6
 An example: SO42-
O
1. Write a possible
arrangement. O S O
O
2. Total the electrons.
6 from S, 4 x 6 from O
add 2 for charge
total = 32
O
||
O - S- O
3. Spread the electrons ||

around. O
Atoms with fewer than eight electrons

Beryllium and boron will both form

compounds where they have less than 8
electrons around them.

: :
: :
:F:B:F:
: :

: :

:Cl:Be:Cl:

: :
:F:
Atoms with fewer than eight electrons

Electron deficient. Species other than hydrogen and

helium that have fewer than 8 valence electrons.

They are typically very reactive species.

F H F H
| | | |
F- B + :N - H F-B-N-H
| | | |
F H F H
 What is VSEPR Theory
Valence Shell Electron Pair Repulsion
This theory assumes that the molecular
structure is determined by the lone pair
and bond pair electron repulsion around
the central atom
 What Geometry is Possible around
Central Atom?
• What is Electronic or Basic Structure?
• Arrangement of electron pairs around the
central atom is called the electronic or
basic structure
• What is Molecular Structure?
• Arrangement of atoms around the central
atom is called the molecular structure
Possible Molecular Geometry
• Linear (180)
• Trigonal Planar (120)
• T-shape (90, 180)
• Tetrahedral (109)
• Square palnar ( 90, 180)
• Sea-saw (90, 120, 180)
• Trigonal bipyramid (90, 120, 180)
• Octahedral (90, 180)
Molecular Structure from VSEPR
Theory
• H2O Bent or angular
• NH3 Pyramidal
• CO2 Linear
Molecular Structure from VSEPR
Theory
• SF6 Octahedral
• PCl5 Trigonal bipyramidal
• XeF4 Square planar
 What is a Polar Molecule?
• Molecules with unbalanced electrical
charges
• Molecules with a dipole moment
• Molecules without a dipole moment are
called non-polar molecules
 How do you a Pick Polar
Molecule?
• Get the molecular structure from VSEPR
theory
• From (electronegativity) difference of
bonds see whether they are polar-covalent.
• If the molecule have polar-covalent bond,
check whether they cancel from a
symmetric arrangement.
• If not molecule is polar
 Which Molecules are Polar
• H2O Bent or angular, polar-covalent
bonds, asymmetric molecule-polar
• NH3 Pyramidal, polar-covalent bonds,
asymmetric molecule-polar
• CO2 Linear, polar-covalent bonds,
symmetric molecule-polar
What is Valence Bond Theory
• Describes bonding in molecule using
atomic orbital
• orbital of one atom occupy the same
region with a orbital from another atom
• total number of electrons in both orbital is
equal to two
sp2 and sp3 Hybridization
What are  and  bonds

 bonds
single bond resulting from head to head
overlap of atomic orbital

 bond
double and triple bond resulting from lateral or
side way overlap of atomic orbitals
What is hybridization?

Mixing of atomic orbitals on the central atom

Bonding
a hybrid orbital could over lap with another atomic orbital or hybrid

orbital of another atom to make a covalent bond.

possible hybridizations: sp, sp2, sp3, sp3d, sp3d2

How do you tell the hybridization of a central
atom?

•Get the Lewis structure of the molecule

•Look at the number of electron pairs on the
central atom. Note: double, triple bonds are
counted as single electron pairs.
•Follow the following chart
Kinds of hybrid orbitals

Hybrid geometry # of orbital

sp linear 2
sp2 trigonal planar 3
sp3 tetrahedral 4
sp3d trigonal bipyramid 5
sp3d2 octahedral 6
Hybridization involving d orbitals
•Co(NH3)63+ ion Co3+: [Ar] 3d6
•Co3+: [Ar] 3d6 4s0 4p0

•Concentrating the 3d electrons in the dxy, dxz, and dyz

orbitals in this subshell gives the following electron

configuration hybridization is sp3d2

 Molecular Orbital Theory
• Molecular orbitals are obtained by combining
the atomic orbitals on the atoms in the
molecule.
Bonding and Anti-bobding Molecular Orbital
 Basic Rules of Molecular Orbital Theory
The MO Theory has five basic rules:
• The number of molecular orbitals = the number of
atomic orbitals combined
• Of the two MO's, one is a bonding orbital (lower energy)
and one is an anti-bonding orbital (higher energy)
• Electrons enter the lowest orbital available
• The maximum # of electrons in an orbital is 2 (Pauli
Exclusion Principle)
• Electrons spread out before pairing up (Hund's Rule)
 Bond Order

• Calculating Bond Order

Homo Nuclear Diatomic Molecules
Period 1 Diatomic Molecules: H2 and He2
Homo Nuclear Diatomic Molecules
Period 2 Diatomic Molecules and Li2 and Be2
Homo Nuclear Diatomic Molecules
Molecular Orbital diagram for

O2, F2 and Ne2

Molecualr Orbital diagram for

B2, C2 and N2
Homonuclear Diatomic Molecules
2nd Period
 Electronic Configuration of molecules
When writing the electron configuration of an atom,
we usually list the orbitals in the order in which
they fill.
Pb: [Xe] 6s2 4f14 5d10 6p2
We can write the electron configuration of a
molecule by doing the same thing. Concentrating
only on the valence orbitals, we write the electron
configuration of O2 as follows.
O2: (22(2*) 2 (24 (2*2
Electronic Configuration and bond order
Hetero Nuclear Diatomic Molecules
HF molecule
Hetero Nuclear Diatomic Molecules
• Carbon monoxide CO
 Panjang Ikatan Kovalen

δ+ δ–
H F

Persamaan Schomaker-Stevenson:

r A-B = r A + r B – 9 │XA – XB│

Conjugated and aromatic molecules

• trans-1,3-Butadiene
• Allyl radical
• Cyclopropenium ion: C3H3+
• Cyclobutadiene
• Cyclopentadiene
• Benzene
• C7H7+ (tropyllium) and C8H82+
trans-1,3-Butadiene
Allyl radical
Cyclopropenium ion:
C3H3 +
Cyclopentadiene
Benzene
Aromatic Rings
The Isolobal Analogy
• Different groups of atoms can give
rise to similar shaped fragments.
Metallic Bonding

• Metals are held together by delocalized bonds

formed from the atomic orbitals of all the atoms in
the lattice.
• The idea that the molecular orbitals of the band of
energy levels are spread or delocalized over the
atoms of the piece of metal accounts for bonding
in metallic solids.
Bonding Models for Metals
•Band Theory of Bonding in Solids
•Bonding in solids such as metals, insulators and
semiconductors may be understood most
effectively by an expansion of simple MO theory to
assemblages of scores of atoms
Linear Combination of Atomic Orbitals
Linear Combination of Atomic Orbitals
Types of Materials
• A conductor (which is usually a metal)
is a solid with a partially full band
• An insulator is a solid with a full band
and a large band gap
• A semiconductor is a solid with a full
band and a small band gap
• Element Band Gap
C 5.47 eV
Si 1.12 eV
Ge 0.66 eV
Sn 0 eV
 Superconductors
• When Onnes cooled mercury
to 4.15K, the resistivity
suddenly dropped to zero
 The Meissner Effect
•Superconductors show perfect
diamagnetism.
•Meissner and Oschenfeld discovered that
a superconducting material cooled below its
critical temperature in a magnetic field
excluded the magnetic flux.Results in
levitation of the magnet in a magnetic field.
Theory of
Superconduction
•BCS theory was proposed by J. Bardeen,
L. Cooper and J. R. Schrieffer. BCS
suggests the formation of so-called 'Cooper
pairs' Cooper pair formation -
electron-phonon
interaction: the electron is
attracted to the positive
charge density (red glow)
created by the first electron
distorting the lattice
around itself.
High Temperature
Superconduction
•BCS theory predicted a theoretical maximum to
Tc of around 30-40K. Above this, thermal energy
would cause electron-phonon interactions of an
energy too high to allow formation of or sustain
Cooper pairs.

• 1986 saw the discovery of high temperature

superconductors which broke this limit (the
highest known today is in excess of 150K) - it is in
debate as to what mechanism prevails at higher
temperatures, as BCS cannot account for this.