Valence Bond (VB) Theory for Main-

Group Elements
 Valence Bond (VB) Theory

•The basic principle of VB theory - A covalent bond forms when the orbitals of two atoms overlap and a pair of
electrons occupy the overlap region.
•The space formed by the overlapping orbitals can accommodate a maximum of two electrons and these
electrons must have opposite (paired) spins.
•The greater the orbital overlap, the stronger the bond. Extent of orbital overlap depends on orbital shape and
direction.
Figure 11.1 Orbital orientation and maximum overlap.
 Valence Bond (VB) Theory for Main-Group Elements

•Both VSEPR model and VB theory are extensively used for the molecules of main-group elements.
•VSEPR model and VB theory go hand-in-hand — we use the VSEPR model to explain the shapes of the molecules
and VB theory to explain bonding.
•According to VB theory, the atomic orbitals first mix together to form hybrid orbitals. The process is referred to
as hybridization.
•The hybrid orbitals then overlap with the orbitals of the adjacent atoms to form covalent bonds.
 Why do we need hybrid orbitals to explain bond-formation?

•The atomic p orbitals are perpendicular to each other, and so they fail to describe the different shapes of
molecules.

•The mixed atomic orbitals or hybrid orbitals can efficiently describe the various bond angles (e.g. 120 degrees in
BCl3, 109.5 degrees in CH4, etc.) of a molecule.
 Key Features of Hybrid Orbitals

•The number of hybrid orbitals formed equals the number of atomic orbitals mixed.
e.g. four sp3 hybrid orbitals are formed by mixing four different atomic orbitals — one s and three p orbitals.
•The number of hybrid orbitals matches the number of electron-groups. Single/Double/Triple bonds and lone
electron pairs count as electron-groups.
•The shape and orientation of a hybrid orbital maximizes overlap with the other atom in the bond and minimizes
electron-electron repulsion.
 sp hybrid orbitals
 Beryllium Chloride (BeCl2)
4Be →

17 Cl →
 sp2 hybrid orbitals
 Boron trifluoride (BF3)
B→
5

9 F→
 sp3 hybrid orbitals
 Methane (CH4)
C→
6

1 H→
 Another Example of sp3 hybrid orbitals
 Water (H2O)
O→
8

H→
1
 Orbital Overlap
Sigma (σ) and Pi (π) Covalent Bonds
 Sigma (σ) Bond
 A sigma (σ) bond is formed by end-to-end or head-on overlap of
orbitals.
 All single bonds are σ bonds.

s bond formed by s-sp3

both C atoms are sp 3
overlap
hybridized

Ethane (C2H6)
End-to-end sp -sp overlap to
3 3

form a s bond
 Pi (π) Bond
 A pi (p) bond is formed by sideways overlap of unhybridized p orbitals.

 A p bond is weaker than a σ bond because sideways overlap is less

effective than end-to-end overlap.

 A double bond consists of one σ bond and one p bond.

Ethene (C2H4)
 Triple Bond

 A triple bond consists of one σ bond and two p bonds.

Ethyne (C2H2)