PHOTOCHEMISTRY WEEK 2 L-1

PHOTOCHEMISTRY
WEEK 2, L-1
PRESENTED BY
Dr Shaista Taimur
DEPARTMENT OF CHEMISTRY
Fatima Jinnah Women University
Rawalpindi
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Disclaimer:

“In preparation of course materials different online sources in the

shape of books, websites, research papers and presentations etc are
used. However, the author does not have any intention to take any
benefit of these in her/his own name. This lecture (audio, video, slides
etc) is prepared and delivered only for educational purposes and is not
intended to infringe upon the copyrighted material. Sources have been
acknowledged where applicable. The views expressed are presenter’s
alone and do not necessarily represent actual author(s) or the
institution.”
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TODAY’S OUTCOMES
• MOLECULAR ORBITALS (REVISION)
• BONDING, ANTIBONDING, NONBONDING
• FORMALDEHYDE- MOT
• HOMO, LUMO (FRONTIER MOs)
• TYPES OF ELECTRONIC TRANSITIONS AND STATES
• n → π*
• π → π*
• S0 → S1
• S0 → T 1
• Spin multiplicity of the ground state and excited states of methanal
• STATE DIAGRAM
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Molecular Orbital Theory
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Molecular orbitals

ψ*AB = ψA - ψB

ψAB = ψA + ψB
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Molecular orbitals
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Higher - energy antibonding molecular orbitals

Nonbonding molecular orbitals generally have

a higher energy than bonding orbitals

Lower - energy bonding molecular orbitals

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FORMALDEHYDE
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FORMALDEHYDE
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PHOTON ABSORPTION-The possible electronic configurations that can occur in
ground - state and excited - state methanal molecules.
• The ground - state methanal has a closed
shell structure (occupied molecular
orbitals all contain two paired electrons)
• HOMO is the nonbonding n molecular
orbital localised on the O atom of the
carbonyl group
• LUMO is the antibonding π*molecular
orbital of the CO group.
• Neglecting the filled low - energy σ -
orbitals, the electronic configuration of the
lowest electronic state (the ground state) is
π2n2.
• n → π* (HOMO → LUMO) leads to π2nπ*
• π → π* leads to πn2π*excited
configurations.
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Spin multiplicity of the ground state and excited states of methanal
• The ground state is a singlet state (S0)
• The excited states being either singlets (S1, S2, etc.) or triplets (T1, T2, etc.) (Figure 1.10 ).
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• S1 and T1 excited states arise from the promotion of an

electron from the n molecular orbital to the π*
molecular orbital, referred to as 1(n, π* ) and 3(n, π* )
states.

• The S2 and T2 states arise from the promotion of an

electron from the π molecular orbital to the π*
molecular orbital, referred to as 1( π , π* ) and 3( π , π*)
states.
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• An excited triplet state always has a lower energy than

that of the corresponding excited singlet state. This is in
line with Hund ’ s rule : when two unpaired electrons
occupy different orbitals, there is a minimum energy
repulsion between the electrons when their spins are
parallel.

• S0 → S1 transitions: When electron excitation of a ground

- state molecule, S0, occurs, there is a tendency for the
spin multiplicity to be retained.
• S0 → T1 transitions: are said to be spin forbidden; that is,
they may be allowed but tend to be much less probable
than S0 → S1 transitions.
• Triplet excited states are generally accessed from the S1
state only if the molecule or its environment favors the
process of INTERSYSTEM CROSSING (ISC), whereby a
molecule in the S1 state is converted to a triplet state.
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For octahedral complexes of Ru(III), and other d6 ions, the σL and πL MOs are fully occupied and the ground - state
configuration is a closed shell because the HOMO πM is fully occupied ( t2g6 ). The ground state is a singlet state (S0),
with the excited states being either singlets or triplets (Figure 1.12 )
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