Valence Bond Theory (VBT) Molecular Orbital Theory (MOT)
Valence orbital theory was first-1 Molecular orbital theory was proposed
proposed by W.Heitler and by F. Hund and R.S. Mulliken
.F.London
The valence bond theory explains-2 The molecular orbital theory is based
..the bonding of atomic orbitals on the molecular orbitals
.describes hybrid orbitals-3 describes bonding molecular orbitals
.and antibonding molecular orbitals
Resonance plays an important role-4 There is no place of resonance in this
.in this theory .theory
There is no explanation of-5 Good explanation of paramagnetic
.paramagnetic character of oxygen .character of oxygen
.Calculations are simpler -6 Calculations are very difficult
Atomic orbitals: orbitals that are localized on
single atoms.
Molecular orbitals: orbitals that span two or more
atoms. Constructing molecular orbitals (MOs) by
overlapping atomic orbitals (AOs)
bonds: electron density of MO directed along
bond axis
bonds: electron density of MO has a nodal plane
that contains the bond axis
Degenerate 2p atomic orbitals
Sigma bonds for a hydrogen molecule
• Sigma bonds can form where two s orbitals overlap.
The sigma bond is cylindrically symmetrical.
Atomic and molecular orbitals of H and H 2
• Before covalent bond formation, each electron is in an atomic orbital.
• After covalent bond formation, both electrons are in the bonding molecular orbital.
• The antibonding molecular orbital is empty.
p Orbital bonding (end-to-end)
• End-on overlap of two p orbitals to form a sigma
bonding molecular orbital and a sigma antibonding
molecular orbital.
p Orbital bonding (side-to-side)
• Side-to-side overlap of two parallel p orbitals to
form a pi bonding molecular orbital and a pi
antibonding molecular orbital.
Constructive and destructive overlap of 2 p orbitals to
form and orbitals
(a) Bonding orbital; (b) Antibonding orbital
Overlap perpendicular to
the internuclear axis is
termed overlap. A nodal
plane that contains the
bond axis. The resulting
orbitals are called and
orbitals
Remember: + and - refer
to mathematical symbols,
not charge
Building up the MOs of simple diatomic molecules
Mix atomic orbitals (AOs) of the same or similar
energies to form molecular orbitals (MOs)
s+s = s + s
px + p x = p + p
pz + p z = p + p
py + p y = p + p
Total of 8 MOs which can hold up to 16 electrons
Bond order (BO): the net number of bonds, allowing for
the cancellation of bonds by anti-bonds
We can deduce molecular stability from BO
BO = 1/2(N - N*) where N = number electrons in
bonding orbitals and N* = number of electrons in anti-
bonding orbitals
Example: (1s)2(1s*)1
N = 2, N* = 1
BO = 1/2(N - N*) =1/2
Any diatomic molecule with BO > 0 is considered
stable relative to the two dissociated atoms.
A shared pair of electrons make a single covalent bond
Electrons in bonding orbitals enhance bonding,
electrons in anti-bonding orbitals reduce bonding
Bond order is a measure of the bonding between two
atoms: 1/2[(e in bonding MOs) - [(e in anti-bonding
MOs)]
Orbital energies for the 3Li-10Ne
The relative energies are bonding sigma < pi < antibonding pi
< antibonding sigma
Switch
Li, Be, B, C, N O,F,Ne
Correlation diagrams for B2 (left) and O2 (right)
VEs)2(s*)2(p)2(p)2 (p*)0(p*)0 VEs)2(s*)2(p)2(p)4 (p*)2 (p*)0
What are the bond orders? What are the magnetic
properties?
Electron configurations for the diatomic molecules:
B2, C2, N2, O2, F2, Ne2
VE: 6 8 10 12 14 16
The molecular orbital electronic configuration of 7N2
Group V: Valence electrons = 10. Ignore core electrons
What is the bond
order of N2?
BO = 1/2(N - N*)
N = 8, N* = 2,
N - N* = 6
BO = 1/2(6) = 3
How does the Lewis
structure compare to
the MO structure?
N N
The molecular orbital electronic configuration of 8O2
Group VI: Valence electrons = 12. Ignore core electrons
What is the electronic
configuration of O2?
(2s)2(*2s)2(2p)2(2p)4(*2p )2
What is the bond order of O2?
Bond order = 1/2(N - N*)
1/2(8 - 4) = 2
O2 possesses a net double
bond and is paramagnetic
Electron configurations of the valence electrons of N2 and O2
Lewis structure Lewis structures
N N O O O O
Paramagnetic: O2: (2s)2(*2s)2(2p)2(2p)4(*2p )2
Diamagnetic: N2: (2s)2(*2s)2(2p)2(2p)4
O2 is paramagnetic
The molecular orbital electronic configuration of 9F2
Group VII: Valence electrons = 14
What is the valence electronic
configuration of F2?
(2s)2(*2s)2(2p)2(2p)4(*2p)4
What is the bond order of
F2?
BO = 1/2(8 - 6) = 1
F2 possesses a net single bond
Molecular orbital configurations of homonuclear diatomics
Bond orders, bond lengths and bond energies
The bond orders from MO theory agree with Lewis
18.2 Polyatomic molecules
Valence bond theory and molecular orbital theory
Valence bond theory: localized bonds, like Lewis structures
Hybridization of orbitals to make stronger bonds
Hybridization and molecular geometry
Hybridization and bond order. Single, double and
triple bonds
Valence bond: Overlap of two s orbitals to
produce a bond
Valence bond: Overlap of an s orbital and a pz orbital to
produce a bond
Valence bond: Overlap of two pz orbitals to produce
a bond
Valence bond: Overlap of two px orbitals to produce a
bond
Hybridization
If more than two atoms are involved in a molecule, the
shapes of the orbitals must match the shape of the
bonds that are needed (trigonal, tetrahedral, etc.).
The atomic orbitals do not have these shapes, and
must be mixed to achieve the needed shapes
Shapes of hybridized atomic orbitals
The hybridization of a s orbital and two p orbitals
to produce three sp2 orbitals
Three
Three hybrid
Atomic Orbitals
orbitals HAOs
Aos sp2
2s + two
2p
The orientations of four sp3 orbitals
The hybridization of a s orbital and a p orbital to
produce two sp hybrid orbitals
2s orbital could be + or -
