1a-Chem Bonding-General Slides for All Sections
1a-Chem Bonding-General Slides for All Sections
1a-Chem Bonding-General Slides for All Sections
Books to Refer:
1. Inorganic Chemistry by Shriver & Atkins
2. Inorganic Chemistry by James E. Huheey
3. WILEY Engineering Chemistry – 2nd Ed. 2013
4. Solid State Chemistry: An introduction, 4th Ed.,
CRC Press.; Moore and Smart.
4th Jan 2021 to 02 Feb 2021 for Inorganic Chemistry (13 h, 26-Jan-21 holiday)
• Bonding and Coordination Chemistry: Bonding in homo- (Li2 to N2 O2 and F2) and
heterodinuclear (only CO). CFT and application of CFT. From Laboratory to Living Systems.
Spectroscopic, magnetic, functional properties of new age coordination compounds, and
Hemoglobin. (5-6 lectures)
• Redox chemistry: Diagrammatic representation and use of Latimer and Frost diagram.
Applications of redox chemistry in energy storage (primary and secondary batteries).
(3 lectures)
• Materials Chemistry: Metal oxides, spinel, superconductor, and boron nitride.
(1-2 lectures)
Important Instruction
• Must attend all the Regular and Tutorial classes
Mode of Evaluation
• 3 (Three) Assignments: Detail instruction will be sent
• B H B +
• A H B +
• B H A
Numerator = 2EA + 2
Looking at the denominator:
E = A+B H A+B/A+B A+B
Denominator = 2(1 + S)
Summing Up . . .
E = A+B H A+B/A+B A+B
Numerator = 2EA + 2
Denominator = 2(1 + S)
E+ = (EA + )/ (1 + S)
Also E- = (EA - )/ (1 – S)
E± = EA ±
S is very small
Neglect S
Energy level diagram
EA -
A B
EA +
Linear combination of atomic orbitals
A B
A B
. + .
+. +.
g bonding
cA = cB = 1
g = N [A + B]
Amplitudes of wave
functions added
2AB = (cA2 A2 + 2cAcB A B + cB2 B 2)
density between atoms
+. -. +. .-
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.
A-B
Amplitudes of wave
functions
subtracted.
The electron is excluded from internuclear region destabilizing
Antibonding
When 2 atomic orbitals combine there are 2
resultant orbitals
orbitals..
Eg.. s orbitals
Eg
*1s
E high energy antibonding orbital
1sb 1sa
1s
Molecular
orbitals
low energy bonding orbital
Molecular potential energy curve shows the variation
of the molecular energy with internuclear separation.
Looking at the Energy Profile
• Bonding orbital
• called 1s orbital
• s electron
• The energy of 1s orbital
decreases as R decreases
• However at small separation,
repulsion becomes large
• There is a minimum in potential
energy curve
H2
11.4 eV
LCAO of n A.O n M.O.
109 nm
Location of
Bonding orbital
4.5 eV
The overlap integral
S A B d
*
S > 0 Bonding S < 0 anti
2-
Cl4Re ReCl4
g- identical B
under inversion
A
u- not identical
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
2s 2s
Energy
2g
1u*
1s 1s
1g
Diatomic molecules: Homonuclear Molecules of the Second Period
Be Be2 Be
2u*
2g
Bond order: 0
1u*
1s 1s
1g
Simplified
Simplified
MO diagram for B2
3u*
1g*
1u
3g
Diamagnetic??
2u*
2g
Li : 200 kJ/mol
F: 2500 kJ/mol
Same symmetry, energy mix-the one with higher energy moves higher
and the one with lower energy moves lower
MO diagram for B2
B B2 B
3u*
3u*
1g*
1g*
2p (px,py)
1u
3g 2p
LUMO 3g
2u*
2s 2s
2g
2g
Paramagnetic
C2
1g 1g
1u
1u
1g
1g
X
Paramagnetic ? Diamagnetic
General MO diagrams
1g 1g
1u
1u
1g 1g
Li2 to N2 O2 and F2
Orbital mixing Li2 to N2
Bond lengths in diatomic molecules
O C