Bonding in Organic Molecules

L2: Molecular Orbital Diagram of Common Organic

Molecules

Dr. Ajoy Kapat/10-01-2024

 Molecular Orbitals from 1s Atomic Orbitals
Formation of molecular orbital from atomic orbital:

Approximate solutions to these molecular Schrödinger equations can be constructed from linear combinations of atomic orbitals (LCAO),
the sums and differences of the atomic wave functions. For diatomic molecules such as H2, such wave functions have the form

where Psi︎ is the molecular wave function, Psia and Psib are atomic wave functions for atoms a and b, and ca and cb are adjustable
coefficients that quantify the contribution of each atomic orbital to the molecular orbital.

The coefficients can be equal or unequal, positive or negative, depending on the individual orbitals and their energies. As the distance
between two atoms is decreased, their orbitals overlap, with significant probability for electrons from both atoms being found in the region
of overlap. As a result, molecular orbitals form.
 Molecular Orbitals from 1s Atomic Orbitals
Formation of molecular orbital from atomic orbital:

- First, the symmetry of the orbitals must be such that regions with the same sign of c overlap.

- Second, the atomic orbital energies must be similar.

- When the energies differ greatly, the change in the energy of electrons upon formation of molecular orbitals is small, and
the net reduction in energy

- The distance between the atoms must be short enough to provide good overlap of the orbitals, but not so short that
repul- sive forces of other electrons or the nuclei interfere.
 Overview of Principles of Molecular Orbitals

Sigma orbital (σ): Sigma star orbital (σ*):

1s 1s 1s 1s

combine in phase combine out of phase

nodal plane
bonding orbital antibonding orbital

- bonding orbital of standard

single bond comprised of two
sp3, sp2 or sp hybrid atomic orbitals

- Cylindrically symmetrical.

- Rotational symmetry along bond axis.

 Overview of Principles of Atomic Orbitals

1s - orbital:
2s - orbital:
 Overview of Principles of Atomic Orbitals

1s - orbital: Different way of representation of 1s - orbital:

Organic Chemistry by Wade

Molecular Orbital Diagram of Hydrogen Molecule
 Overview of Principles of Atomic Orbitals

2p - orbital: Different way of representation of 2p - orbital:

Organic Chemistry by Wade

 Overview of Principles of Molecular Orbitals

Sigma orbital (σ):

2Px 2Px

combine in phase

bonding orbital
 Overview of Principles of Molecular Orbitals

Sigma orbital (σ): Sigma star orbital (σ*):

2Px 2Px 2Px 2Px

- Cylindrically symmetrical.
combine in phase
- Rotational symmetry along bond axis. combine out of phase

bonding orbital nodal plane

antibonding orbital
 Overview of Principles of Molecular Orbitals

Sigma orbital (σ): Sigma star orbital (σ*):

2Px 2Px 2Px 2Px

- Cylindrically symmetrical.
combine in phase
- Rotational symmetry along bond axis. combine out of phase

bonding orbital nodal plane

antibonding orbital
Pi orbital (π):

2PZ 2PZ

combine in phase

bonding orbital
 Overview of Principles of Molecular Orbitals

Sigma orbital (σ): Sigma star orbital (σ*):

2Px 2Px 1s 1s

- Cylindrically symmetrical.
combine in phase
- Rotational symmetry along bond axis. combine out of phase

bonding orbital nodal plane

antibonding orbital
Pi orbital (π): Pi star orbital (π*):

2PZ 2PZ 2PZ 2PZ

combine in phase combine out of phase

- No cylindrically symmetrical.

- plane of symmetry along bond axis.

nodal plane

bonding orbital antibonding orbital

 Molecular Orbitals of Nitrogen
MO Diagram of diatomic molecules
σ*
Molecular Orbital Diagram:
π*z π*y

Z 2Px πz πy Z 2Px
Energy

2Pz 2Pz

X X
σ
2Py 2Py
Y Y
σ*
2s 2s

σ
σ*
1s 1s

atomic orbitals atomic orbitals

σ
 Molecular Orbitals of Nitrogen
MO Diagram of diatomic molecules
σ*
Molecular Orbital Diagram:
π*z π*y

nodal plane

Z 2Px πz πy
Energy

2Pz

X
σ
2Py
Y
σ*
2s 2s

σ
σ*
1s 1s

atomic orbitals atomic orbitals

σ
 Molecular Orbitals of Nitrogen
MO Diagram of N2
σ*
Molecular Orbital Diagram:
π*z π*y

2Px πz πy
Z
Energy

2Pz

X
σ
2Py
Y
σ*
2s 2s

σ
σ*
1s 1s

atomic orbitals nitrogen atomic orbitals of nitrogen

σ
 Molecular Orbitals of Heterodiatomic Molecules

Molecular Orbital Diagram AX:

MO Diagram of AX
σ* Z 2Px
2Pz

π*z π*y X

2Py
Y
Z 2Px
2Pz
πy
Energy

πz 2P
X

2Py
Y σ
σ*
2s 2s

atomic orbitals of A atomic orbitals of X

 Molecular Orbitals of Heterodiatomic Molecules

Molecular Orbital Diagram:

MO Diagram of NO
σ* Z 2Px
2Pz

π*z π*y X

2Py
Y
Z 2Px
2Pz
πy
Energy

πz 2P
X

2Py
Y σ
σ*
2s 2s

atomic orbitals nitrogen atomic orbitals of oxygen

 Molecular Orbitals of Heterodiatomic Molecules

Molecular Orbital Diagram:

MO Diagram of NO
σ*

1 1 1
π*z π*y
2Pz 2Py 2Px
Energy

2Px2 2Py1 2Py1

πz πy 2P

σ
σ*
2s 2s

Electronegativity of N (3.04) σ* Electronegativity of O (3.44)

atomic orbitals nitrogen atomic orbitals of oxygen
 Molecular Orbitals of Heterodiatomic Molecules

Molecular Orbital Diagram:

MO Diagram of NO
AO of nitrogen contribute more to the antibonding MO σ*
Antibonding orbitals are closer to Nitrogen atom

1 1 1
π*z π*y
2Pz 2Py 2Px
Energy

2Px2 2Py1 2Py1

πz πy 2P
Bonding orbitals are closer to Oxygen atom
AO of oxygen contribute more to the bonding MO
σ
Antibonding orbitals are closer to Nitrogen atom σ*
2s 2s

Bonding orbitals are closer to Oxygen atom

σ
Electronegativity of N (3.04) Electronegativity of O (3.44)
atomic orbitals nitrogen atomic orbitals of oxygen
 Molecular Orbitals of Heterodiatomic Molecules (Ionic Compound)

Molecular Orbital Diagram of NaCl:

MO Diagram of NaCl

3P

3S
Energy

No interaction

3P

3S

Electronegativity of Na (0.93) Electronegativity of Cl (3.16)

atomic orbitals of Sodium atomic orbitals of Chlorine
 Molecular Orbitals of Heterodiatomic Molecules (Ionic Compound)

Molecular Orbital Diagram of NaCl:

MO Diagram of NaCl

Bond between Na and Cl

3P is purely ionic

3S
Energy

AO of Na contribute more to the antibonding MO

Antibonding orbitals are closer to Na atom

No interaction Bonding orbitals are closer to Cl

AO of Cl contribute more to the bonding MO

electrons in the filled orbital are located to Cl

3P

3S

Electronegativity of Na (0.93) Electronegativity of Cl (3.16)

atomic orbitals of Sodium atomic orbitals of Chlorine