Valence bond Theory

Simple Approximate Theory for Molecules Explains VSEPR Easily visualized

Bonds result from the sharing of electrons in

overlapping atomic orbitals from two different atoms

Electrons are localized in the bonds between the two atoms These orbitals may be pure atomic orbitals or
hybridized atomic orbitals of individual atoms

Valence Bond Theory

Recall
Constructive interference

Destructive interference

s+p

s-p

s and p combine

2 sp hybrid orbitals.

The 2 sp hybrid orbitals point in opposite directions (180 apart). Note, the number of orbitals is conserved. This is always true.

BeH2 (Linear)

(sigma) bonds
(Electron density of bond directly between the two atoms)

(Arrows backwards)

Noteboth take energy

Note: Orbitals, typically drawn more slender than they actually are.

AX2 Linear sp hybrid orbitals AX3 Trigonal planar sp2 hybrid orbitals ? AX4 Tetrahedral ? 3 hybrid orbitals sp AX5 Trigonal bypyramidal sp3d hybrid orbitals ?

AX6 Octahedral ? 3d2 hybrid orbitals sp

ENRICHMENT

D1 = 1/ 2

D2

( )(s + p ) = (1/ 2 ) ( s p )
x

T2

3 degenerate orbitals

Note: lone pairs of electrons on F and vacant pz orbital on B are not shown.

What kind of bonds are formed?

(sigma) bonds

Bond type ?

bond

sp3 hybridization

Bond type ?

Bond type ?

More examplespolyatomic ions

LONE-PAIR ELECTRONS TREATED LIKE BONDING PAIR

NH3

NF3

LONE-PAIR ELECTRONS TREATED LIKE BONDING PAIR

Name for shape? Trigonal pyramidal

sp3 hybridization Hybridization ?

sp3 hybridization Hybridization ?

LONE-PAIR ELECTRONS CONTRIBUTE TO DIPOLE MOMENT

NF

= 0.2 D

= 1.5 D

Digression: Remembermolecules real and have properties

Dry NI3

NI3, like NF3, has sp3 hybridization.

Chemical properties . . .

+ mild shock N2 +I2

Number of lone and bonding pairs of 4 electrons: ? (Steric number) Geometry: ?bent

sp Hybridization: ? 3

Bond angle 104.5

Dipole moment?

Number of lone and bonding pairs of electrons: 4

Hybridization: sp3

ENRICHMENT

Number of lone and bonding pairs of electrons: ? 4 (Steric number)

Expected Hybridization: sp3 ?

Experimental bond angle: 92

What does it imply? Very little hybridization. Why? 1. S atom is larger, so lone pairs are farther apart. 2. It takes energy to form hybrid orbitals. Molecules do what minimizes energy H2Se ?91 H2Te ?90

PCl5

P [Ne]

Bond type ?

bond

SF6
Octahedral

__ __ __ 3d

SF6

Bond type ?

bond

sp

sp2 sp3

sp3d

sp3d2

MULTIPLE BONDS Name? Ethylene or ethene : Single bonds for single Hybridization on C: sp2 bonds?

Top view of sp2 hybrid orbitals

Side view including p orbital

MULTIPLE BONDS Name? Acetylene or ethyne : Hybridization on C: sp bonds? Single bonds for single

H:C:::C:H or HCCH

FE4

3 bonds

How bonds are formed