Contours and energies of H2 bonding and antibonding MOs.

The bonding MO is lower in energy and the antibonding MO is higher in

energy than the AOs that combined to form them.

11-1
 Molecular Orbital Diagrams

An MO diagram, just like an atomic orbital diagram,

shows the relative energy and number of electrons in
each MO.

The MO diagram also shows the AOs from which each

MO is formed.

Bond order is calculated as follows:

½[(No. of e- in bonding MO) – (No. of e- in antibonding MO)]

11-2
 Electron filling in Molecular Orbital (up to 14 electrons)

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 (π2Px)2 = (π2py)2 (σ2pz)2 (π*2Px)2 = (π*2py)2 (σ*2pz)2

Increasing energy Degenerate Increasing Degenerate Increasing

energy energy

Electron filling in Molecular Orbital (More than 14 electrons)

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 (σ2pz)2 (π2Px)2 = (π2py)2 (π*2Px)2 = (π*2py)2 (σ*2pz)2

11-3
Relative MO energy levels for Period 2 homonuclear diatomic
molecules. (σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) = (π2py)
(σ1s) (σ*1s) (σ2s) (σ*2s) (σ2pz) (π2Px)
=

(π2py) (σ*2pz) (π*2Px) = (π*2py) (σ2pz) (π*2Px) =

(π*2py) (σ*2pz)

without 2s-2p with 2s-2p

mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2

11-4
 Electrons in Molecular Orbitals

Electrons are placed in MOs just as they are in AOs.

• Aufbau’s principle: MOs are filled in order of increasing energy.

• Pauli’s exclusion principle: An MO can hold a maximum of 2 e-

with opposite spins.

• Hund’s rule of maximum multiplicity: Pairing of electrons doesn’t

take place until all the atomic or molecular orbital are singly
occupied.
A molecular electron configuration shows the type of MO and the
number of e- each contains. For H2 the configuration is (σ1s)2.

11-5
 MO diagram for H2

(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =

(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)

(σ1s)2

H2 bond order = ½ (2 − 0) = 1

11-6
Stability of molecules in terms of bonding and antibonding electrons

11-7
 Stability of molecule in terms of bond order

11-8
Nature of bond and bond length in terms of bond order

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

Bond length is inversely proportional to the bond order. Greater the bond
order shorter is the length.

Bond strength is inversely proportional to the bond length or

Bond order is directly proportional to bond strength

11-9
 Paramagnetic and diamagnetic nature of molecule

11-10
 MO diagram and electronic configuration for He2+ and He2.
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =
(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)

(σ1s)2(σ *1s )1 (σ1s)2(σ

* 2
1s)

He2+ bond order = ½ (2-1) = ½

He2 bond order = ½ (2-2) = 0
Unpaired electrons = 1 = Paramagnetic
Doest not exist

11-11
 Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to find bond orders and predict

whether H2+ and H2− exist. If either exists, write its
electron configuration.
PLAN: Since the 1s AOs form the MOs, the MO diagrams are similar
to the one for H2. We find the number of electrons in each
species and distribute them one at a time to the MOs following
the rules for orbital filling. We calculate the bond order and
predict stability.
SOLUTION:

H2+ has one electron to place in its MOs while H2- has three electrons
to place.

11-12
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px)
For H2+, the bond order is
½(1 – 0) = ½;
so we predict that H2+ exists.
The configuration is (σ1s)1.
Paramagnetic
11-13
=
(π2py) (σ2pz) (π*2Px) = (π*2py) (σ*2pz)
For H2-, the bond order is
½(2 – 1) = ½;
so we predict that H2- exists.
*
The configuration is (σ1s)2(σ1s )1
 Electronic configuration bond order, bond length and
bond energy of some simple diatomic molecules

11-14
 Bonding in homonuclear diatomic molecules.

(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =

(π2py) (σ2pz) (π*2Px) = (π*2py) (σ*2pz)

(σ1s)2 (σ*1s)2 (σ2s)2

Li2 bond order ½ (4-2) = 1 (Exist)
Diamagnetic

Li2

11-15
 Be2
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =
(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2

Be2 bond order = 0 (Does not exist)
No. of unpaired electrons = 0

• B
e2
11-16
 B2
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =
(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)
KK/

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s) 2 (π2Px) 1 =

(π2py) 1

B2 bond order = ½ (6 − 4) = 1
It exist
Unpaired electrons = 2
Paramagnetic

11-17
 C2
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =
(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)

(σ1s)2 (σ*1s) 2 (σ2s) 2 (σ*2s) 2 (π2Px) 2 =

(π2py) 2

C2 bond order ½ (8-4) = 2 (Does exist)

No. of Unpaired electrons = 0
Diamagnetic

11-18
 Nitrogen molecule (N2)
• Nitrogen molecule (N2) = N + N = 14
• The electronic configuration of nitrogen (Z=7) =
1s2 2s2 2px12py12pz1.
• The total number of electrons present in the nitrogen
molecule (N2) is 14.
• In order to maximize energy, these 14 electrons can be
accommodated in the different molecular orbitals.

• N2: KK(σ2s)2 (σ*2s)2 (π2Px)2 = (π2py)2 (σ2pz)2

• Here (σ1s)2 (σ*1s)2 part of the configuration is abbreviated

as KK’, which denotes the K shells of the two atoms.
• In calculating bond order, we can ignore KK’, as it includes
two bonding and two antibonding electrons.
• The bond order of N2can be calculated as follows:
• Here, Nb = 10 and Na = 4, Bond order = (Nb−Na) /2
• B.O = (10−4)/2 = B.O = 3
• Diamagnetic
11-19
 N2+
(σ1s) (σ*1s) (σ2s) (σ*2s) (π2Px) =
(π2py) (σ2pz) (π*2Px) =
(π*2py) (σ*2pz)

• Total no. of electrons = 13

• N2:
(σ1s)2 (σ*1s)2(σ2s)2 (σ*2s)2 (π2Px)
2
(π2py) 2 (σ2pz) 1

• Here, Nb = 9 and Na = , 4
• Bond order = (Nb−Na) /2
• = 2.5
• No. of unpaired electrons = 1
• Paramagnetic

11-20
 N2-
• (σ1s)2 (σ*1s)2(σ2s)2 (σ*2s)2 (π2Px)2 (π2py)2 (σ2pz)2 (π*2Px)1 = (π*2py)0
(σ*2pz)0

Total no. of electrons = 15

N2:
N2-(σ1s)2 (σ*1s)2(σ2s)2 (σ*2s)2 (π2Px) 2 (π2py)
2
(σ2pz) 2 (π*2Px)1

Here, Nb = and Na = ,
Bond order = (Nb−Na) /2
= 10-5 = 2.5
No. of unpaired electrons = 1
paramagnetic

11-21
 N2 2-

• (σ1s)2 (σ*1s)2(σ2s)2 (σ*2s)2 (π2Px)2 (π2py)2 (σ

2pz)2 (π*2Px)1 = (π*2py)1 (σ*2pz)0
• Here, Nb = and Na = ,
• Bond order = (Nb−Na) /2
• = 10-6 = 2
• No. of unpaired electrons = 2
• Paramagnetic

11-22
 Arrange in the increasing order of
(i) stability and (ii) bond length (iii) Magnetic
property
• N2, N2+ N2- N22-

• Bond order = N2, N2+ N2- N22-

• Bond length = N2, < N2+ < N2- < N22-
• Stability: = N2, > N2+ > N2- > N22-
• Magnetic

11-23
 Electron filling in Molecular Orbital (up to 14 electrons)

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 (π2Px)2 = (π2py)2 (σ2pz)2 (π*2Px)2 = (π*2py)2 (σ*2pz)2

Electron filling in Molecular Orbital (More than 14 electrons)

(σ1s)2 (σ*1s)2 (σ2s)2 (σ*2s)2 (σ2pz)2 (π2Px)2 = (π2py)2 (π*2Px)2 = (π*2py)2 (σ*2pz)2

11-24