Inorganic Chemistry

Books to follow
Inorganic Chemistry by Shriver & Atkins
Inorganic Chemistry by James E. Huheey
Inorganic Chemistry by Gary L. Miessler
Inorganic Chemistry by Catherine E. Housecroft

C. R. Raj
405, A-block, PCR-JCG Building, Department of Chemistry

Section 19 & 20
Theory classes…

September 6 7 8 13 14 15 Mid sem exam 27 29

October 4 5 6 11
 Tutorial Classes

What to do in Tutorial Classes?

Doubt clearing/additional discussion/Question-Answer

Section Day and Time TA’s name Room No

19 (A+B) Wednesday 09 to 09.55 AM LOKNATH THAPA F131

19 (C+D) Wednesday 09 to 09.55 AM SANTANU GHORA F132

20 (A+B) Wednesday 08 to 08.55 AM POULAMI DUTTA F235

20 (C+D) Wednesday 08 to 08.55 AM AKASH MUKHRAJ F236

PASWAN
Chemical Bonding
The three models of chemical bonding
 Chemical Bonding – a quick glance
Valance Bond Theory
A covalent bond forms when the orbitals of two atoms overlap and are occupied by
a pair of electrons that have the highest probability of being located between the
nuclei.

Linus Carl Pauling

(1901-1994)
Nobel prizes: 1954, 1962

Octahedral Complex
e.g. [Cr(NH3)6]3+
Molecular Orbital Theory

Overlap of atomic orbital

Mulliken & Hund
 Chemical Bonding
Valence Bond Theory (VBT) Molecular Orbital Theory (MOT)

Limitations Limitations of VB theory

Cannot account for colour of complexes
Localized bond
May predict magnetism wrongly
Bonding in complex molecules Cannot account for spectrochemical series

MO theory
MOT starts with the idea that the quantum mechanical principles applied to atoms may
be applied equally well to the molecules
It provides a more accurate picture of the electronic structure of molecules and it gives
us more information about their chemistry (reactivity).
 MO Theory
Describe each electron in a molecule by a certain wave function  -
Molecular Orbital (MO).
Each  is defined by certain quantum numbers, which govern its
energy and its shape.
Each  is associated with a definite energy value.
Each electron has a spin, ± ½ and labeled by its spin quantum
number ms.
When building the molecule- Aufbau Principle (Building Principle)
- Pauli Exclusion Principle.
MOs – linear combination of atomic orbitals (LCAO)
 Linear combination of atomic orbitals

Rules for linear combination

1. Atomic orbitals must be roughly of the same energy.

2. The orbital must overlap one another as much as possible- atoms must
be close enough for effective overlap.

3. In order to produce bonding and antibonding MOs, either the symmetry

of two atomic orbital must remain unchanged when rotated about the
internuclear line or both atomic orbitals must change symmetry in identical
manner.
 Energy level diagram
EA - 

A B


EA + 
Coulomb Integral (E) – ground state energy
Resonance integral (β) – measure of the strength of bonding interaction
Overlap integral (S) – extent of overlap
(it magnitude always less than one , i.e. S<<1)
 Rules for the use of MOs
* When two AOs mix, two MOs will be produced

* Each orbital can have a total of two electrons (Pauli principle)

* Lowest energy orbitals are filled first (Aufbau principle)

* Unpaired electrons have parallel spin (Hund’s rule)

Bond order = ½ (bonding electrons – antibonding electrons)

 Linear Combination of Atomic Orbitals (LCAO)

The wave function for the molecular orbitals can be approximated by taking linear combinations of atomic orbitals.

A B
A B

AB = N(cA A + cBB) c – extent to which each AO

contributes to the MO
2AB = (cA2 A2 + 2cAcB A B + cB2 B 2)
Overlap integral
Probability density contribution to the probability density arising
from the interference
 Constructive interference

+. +. . + .

g
cA = cB = 1 bonding

g = N [A + B]

Amplitudes of wave
functions added
The accumulation of electron density between the nuclei put the electron in a position
where it interacts strongly with both nuclei.

Nuclei are shielded from each other

The energy of the molecule is lower

 A second MO can be obtained via subtraction of two AOs
node

+. -. +. .-
cA = +1, cB = -1 u
antibonding
u = N [A - B]
Destructive interference

Nodal plane perpendicular to the H-H bond axis

(en density = 0)
Energy of the en in this orbital is higher

Amplitudes of wave
functions
subtracted.
 H2

11.4 eV
LCAO of n A.O  n M.O.
109 nm

Location of
Bonding orbital
Dissociation
energy
4.5 eV
 S > 0 Bonding S < 0 anti

Bond strength depends on the

degree of overlap S = 0 nonbonding
 Homonuclear Diatomics
• MOs may be classified according to:
(i) Their symmetry around the molecular axis.
(ii) Their bonding and antibonding character.
(iii) The atomic orbitals into which they separate at large
internuclear distances.
• 1s 1s* 2s 2s* 2p y(2p) = z(2p) y*(2p) =z*(2p)2p*.
 dxy and dx2-y2

The in-phase bonding combination has four areas of electron density above and below the
two nuclei, with a vertical and a horizontal node along the internuclear bond axis. In the
out-of-phase combination there is a third node bisecting the internuclear axis
-orbitals
dx2-dy2 and dxy

2-
Cl4Re ReCl4
 Orbital parity – gerade (g) and ungerade (u)

s-orbital p-orbital d-orbital

gerade (g) ungerade (u) gerade (g)
 Orbital parity – gerade (g) and ungerade (u)

a not a
center of center of inversion a
a a≠b
inversion
a=b
b b b

s-orbital p-orbital d-orbital

gerade (g) ungerade (u) gerade (g)
 Parity (g or u) of molecular orbitals:

a a
not a center center of Inversion
of inversion a=b
a≠b b
(sign of wave- b
function is
opposite)
σ*(1s)u π*(2p)g

a a
not a center of
inversion
a≠b
b b
center of inversion
a=b
σ(1s)g π(2p)u
o
The test for whether an MO is g or u is to find the possible center of inversion of the MO. If two lines drawn out at 180 to each other
from the center, and of equal distances, strike identical points (a and b), then the orbital is g.
Labeling molecular orbitals
as g or u:
The following little table will help you to label molecular orbitals as g or u. For σ-
overlap, the bonding orbitals are g, while the antibonding orbitals are u, while for
π–overlap the opposite is true:

bonding MO anti-bonding MO

σ-bonding g u

π-bonding u g
Place labels g or u in this diagram

*u

*g

u

g
 First period diatomic molecules
H H2 H 1s2

u*
Bond order: 1
Energy

1s 1s

g

Bond order = ½ (bonding electrons – antibonding electrons)

 Diatomic molecules: The bonding in He2

He He2 He
1s2, *1s2

u*
Bond order: 0
Energy
1s 1s

g

Molecular Orbital theory is powerful because it allows us to predict whether molecules should
exist or not and it gives us a clear picture of the of the electronic structure of any hypothetical
molecule that we can imagine.
Simplified
Simplified
MO diagram for B2

Diamagnetic??
Orbital mixing

Li : 200 kJ/mol
F: 2500 kJ/mol
Orbital mixing…

Same symmetry and similar energies !

shouldn’t they interact?

 orbitals mix strongly

* orbitals differ more in energy and mix weakly

When two MO’s of the same symmetry mix

the one with higher energy moves higher and the
one with lower energy moves lower
MO diagram for B2
B B2 B

3u*

1g*

2p (px,py)

2p
LUMO 3g

HOMO 1u

2u*

2s 2s

2g

Paramagnetic
C2

1g 1g

1u
1u

1g
1g

Paramagnetic Diamagnetic
 General MO diagrams

1g 1g

1u
1u

1g 1g

Li2 to N2 O2 and F2
Orbital mixing Li2 to N2
Bond lengths in diatomic molecules

Filling bonding orbitals

Filling antibonding orbitals

A

C
 Photoelectron spectroscopy

Ek= h-I

I = h - Ek = 21.1 eV - Ek

KE e-
h ejected
photoelectron
UV photon
N N
I

N N
ionized molecule

The lower the energy of the electron lies initially,

the greater its ionization energy and hence lower its KE after it is ejected
UV-PES spectrum of N2

σ*u

πg

σg

2g πu

1u σu

1u σg
Distance between b-MO and AO
 Heteronuclear Diatomics….

The energy level diagram is not symmetrical.

The bonding MOs are closer to the

atomic orbitals which are lower in
energy.

The antibonding MOs are closer to

those higher in energy.
MO of CO molecule
MO of CO molecule
CO is a very good ligand!
How does it act?

O C This lone pair is available for

donation to act as ligand.
Nitric Oxide