1. What is an allowed transition? Explain with example.
Definition:
An allowed transition is an electronic transition in a molecule or atom that is permitted by
quantum mechanical selection rules (e.g., spin, angular momentum, and symmetry rules).
Such transitions have significant transition dipole moments, making them likely to occur
and result in strong absorption in a UV-Vis spectrum.
Example:
• In UV-Vis spectroscopy, the π → π* transition in conjugated systems is an allowed
transition. For instance, in benzene, the electrons in the π-bond can absorb UV
light and transition to an anti-bonding π* orbital.
2. What is a forbidden transition? Explain with example.
Definition:
A forbidden transition violates one or more quantum mechanical selection rules. Although
these transitions are "forbidden," they can still occur with very low intensity due to
mechanisms like spin-orbit coupling.
Example:
• n → π* transitions in carbonyl compounds (e.g., acetone) are typically forbidden
because they involve a change in symmetry without a change in spin state. This
results in weak absorption peaks in the UV-Vis spectrum.
3. Which types of electronic transitions are possible in UV-Vis? Which are
allowed & forbidden? Explain with 5 examples in which transitions are
allowed or forbidden.
Types of Electronic Transitions in UV-Vis:
1. σ → σ*: Transition from a bonding σ orbital to an anti-bonding σ* orbital.
2. n → σ*: Transition from a non-bonding (lone pair) orbital to an anti-bonding σ*
orbital.
3. π → π*: Transition from a bonding π orbital to an anti-bonding π* orbital.
4. n → π*: Transition from a non-bonding orbital to an anti-bonding π* orbital.
Allowed vs. Forbidden:
• Allowed:
o Transitions involving a change in symmetry and spin (e.g., π → π*).
• Forbidden:
o Transitions that do not obey symmetry or spin selection rules (e.g., n → π*).
Examples:
1. π → π* (Allowed): Observed in aromatic compounds like benzene.
2. n → π* (Forbidden): Seen in ketones like acetone.
3. σ → σ* (Allowed): Observed in molecules with strong single bonds, like methane.
4. n → σ* (Allowed): Seen in alcohols or amines, where lone-pair electrons transition.
5. d → d (Forbidden): In transition metals, this is spin-forbidden but can occur weakly
due to spin-orbit coupling (e.g., in a d-block metal complex like [Fe(H2O)6]2+).
Here are five examples for each type of electronic transition in UV-Vis spectroscopy,
along with the classification of whether the transition is allowed or forbidden:
1. σ → σ* (Sigma to Sigma Anti-Bonding Transition):
• Description: High-energy transition; occurs in molecules with single bonds.
• Examples:
o Methane (CH₄): Allowed.
o Ethane (C₂H₆): Allowed.
o Propane (C₃H₈): Allowed.
o H₂ molecule: Allowed.
o Chloromethane (CH₃Cl): Allowed.
Reason: These transitions obey symmetry rules and involve strong bonding to anti-bonding
orbital transitions.
2. n → σ* (Non-Bonding to Sigma Anti-Bonding Transition):
• Description: Moderate-energy transition; occurs in molecules with lone-pair
electrons.
• Examples:
o Water (H₂O): Allowed.
o Ammonia (NH₃): Allowed.
o Methanol (CH₃OH): Allowed.
o Hydrogen peroxide (H₂O₂): Allowed.
o Diethyl ether (C₂H₅OC₂H₅): Allowed.
Reason: These transitions involve lone-pair electrons transitioning to anti-bonding orbitals
and are allowed.
3. π → π* (Pi to Pi Anti-Bonding Transition):
• Description: Lower-energy transition; occurs in molecules with double bonds or
aromatic systems.
• Examples:
o Ethene (C₂H₄): Allowed.
o Benzene (C₆H₆): Allowed.
o 1,3-Butadiene (C₄H₆): Allowed.
o Styrene (C₈H₈): Allowed.
o Phenol (C₆H₅OH): Allowed.
Reason: These transitions involve symmetric π to π* transitions, which are allowed by the
selection rules.
4. n → π* (Non-Bonding to Pi Anti-Bonding Transition):
• Description: Typically forbidden; occurs in molecules with lone-pair electrons
adjacent to a π-bond.
• Examples:
o Acetone (CH₃COCH₃): Forbidden.
o Formaldehyde (HCHO): Forbidden.
o Acetamide (CH₃CONH₂): Forbidden.
o Nitromethane (CH₃NO₂): Forbidden.
o Ethyl acetate (CH₃COOC₂H₅): Forbidden.
Reason: These transitions often violate symmetry rules, but they can occur weakly due to
spin-orbit coupling.
5. d → d Transitions (In Transition Metal Complexes):
• Description: Typically forbidden by spin and Laporte selection rules, but can occur
weakly.
• Examples:
o [Fe(H₂O)₆]²⁺ (Iron aqua complex): Forbidden (weak absorption).
o [Cu(H₂O)₆]²⁺ (Copper aqua complex): Forbidden (weak absorption).
o [Co(H₂O)₆]²⁺ (Cobalt aqua complex): Forbidden (weak absorption).
o [Ni(NH₃)₆]²⁺ (Nickel amine complex): Forbidden (weak absorption).
o [Mn(H₂O)₆]²⁺ (Manganese aqua complex): Forbidden (weak absorption).
Reason: These transitions are spin-forbidden and Laporte-forbidden but can occur weakly
due to vibronic coupling.
