Lecture Notes-7-B

HOMO - LUMO
 Conjugation
• Conjugation: Special stability associated with
three or more adjacent, parallel, overlapping p
orbitals, resulting in increased electron
delocalization and longer electron
wavelengths. Not limited to pi-sigma-pi bond
arrangements.
Butadiene: An unsaturated aliphatic hydrocarbon of molecular
formula C4H6.
 Benzene: An aromatic hydrocarbon of formula C6H6,
characterized by a ring of six carbon atoms, bonded by
alternating single and double bonds. A benzene ring with a single
substituent (C6H5-X) is called a phenyl group (Ph).
Furan: An aromatic ether of molecular formula C4H4O,
or a molecule containing this moiety.
N,N-Dimethylformamide (dimethylformamide, DMF): A
polar (ε = 37) aprotic solvent with molecular formula
C3H7NO.
Allyl carbocation: The primary, resonance-stabilized
carbocation with the structure shown below.
 Cyclooctatetraene (1,3,5,7-cyclooctatetraene; COT): An
unsaturated aliphatic hydrocarbon of molecular formula C8H8.
Because of its nonplanarity

Cyclooctatetraene is not conjugated. The

pi bonds are not parallel, so each p
orbital is parallel to just one other p
orbital.
 Resonance
• Resonance: A condition in which a molecule cannot be
adequately represented by a single Lewis structure; two or
more Lewis structures are required.
 Electron delocalization
• Electron delocalization: Distribution of electron density
beyond a fixed place such as a single atom, lone pair, or
covalent bond via resonance or inductive effects.

The oxygen lone pairs of ethoxide ion are not

delocalized.

The oxygen lone pairs of trifluoroethoxide ion

are delocalized via the trifluoromethyl group's
electron-withdrawing inductive effect
 Aromaticity
• Aromaticity: Special molecular stability associated with a
closed loop of adjacent, parallel, overlapping p orbitals which
contains 4n+2 pi electrons (n = 0, 1, 2, 3, etc.)

Aromatic (n = 1)

Not aromatic
 Nonaromatic
• Nonaromatic: A molecule that is neither aromatic or
antiaromatic.

1,3,5-Hexatriene is nonaromatic because it

does not have a closed loop of p orbitals.

Cyclooctatetraene is nonaromatic because the

atoms which host its p orbital loop are not
planar.
 Barrier to rotation
• Barrier to rotation: The difference in energy between the
most stable and least stable conformations when considering
rotation around a bond. It is the energy barrier which must be
overcome for one full rotation around a bond.
• The barrier to rotation for the C2-C3 bond of 1,3-butadiene is
the difference in energies of the s-trans conformation (alkene
dihedral angle = 180o; most stable conformation) and the
conformation in which the alkenes are perpendicular (alkene
dihedral angle = 90o; least stable conformation).
 HOMO-LUMO gap
• HOMO-LUMO gap: The energy difference between a
molecule's Highest energy Occupied Molecular Orbital
(HOMO) and its Lowest energy Unoccupied Molecular Orbital
(LUMO).
 Ground state
• In infrared spectroscopy, absorption of a photon of
energy ΔE causes an excitation from the vibrational
ground state to a vibrational excited state

In infrared spectroscopy,
absorption of a photon of
energy ΔE causes an excitation
from the vibrational ground
state to a vibrational excited
state
 Excitation
• Excitation: The process of changing from a ground state to an
excited state by energy absorption.
• In NMR spectroscopy, absorption of a radio wave photon of
energy ΔE causes excitation from the ground nuclear spin
state (I = +1/2) to the excited nuclear spin state (I = 1-/2).
 Photochemistry
• Photochemistry: The study of chemical processes induced by
the absorption of light (visible or ultraviolet) photons.

Light-induced radical bromination of methane

is a photochemical reaction.
Cis/trans isomerization of azobenzene is a
photochemical reaction.

Intramolecular [2+2] cycloaddition reaction is a

photochemical reaction.
 SOMO
• SOMO: A Singly Occupied Molecular Orbital. A molecular
orbital occupied by just one electron.

Unoccupied

SOMO and HOMO

LUMO
 Diels-Alder
• Diels-Alder reaction: A [4+2] cycloaddition reaction in which a
carbon-carbon pi bond (the dienophile) reacts with a
conjugated 1,3-diene to form a six-membered ring, via a
concerted mechanism.

Diene
Dienophile
• [2+2]: A cycloaddition reaction in which two adjacent atoms
of one reactant add to two adjacent atoms of another
reactant to form a four-membered ring.

An intermolecular [2+2] cycloaddition reaction.

An intramolecular [2+2] cycloaddition reaction.

• [3+2]: A cycloaddition reaction in which a three-atom
component combines with a two-atom component to form a
five-membered ring. May be intermolecular or
intramolecular.

This intermolecular [3+2] cycloaddition of an oxyallyl cation (the three

atom component; shown in red) with an alkyne (the two atom
component; shown in blue) produces a new cyclopentane ring.
• [4+3]: A cycloaddition reaction in which a four-atom
component combines with a three-atom component to form a
new seven-membered ring. The reaction may be
intermolecular or intramolecular.

In this intermolecular [4+3] cycloaddition reaction, furan (the four-

atom component; shown in red) combines with an oxyallyl cation (the
three-atom component; shown in blue) to form a new cycloheptane
ring.
 ΔE
• ΔE: An energy difference. In Chem 14C and Chem 14D refers
to the energy difference between quantum mechanical
energy states (rotational, vibrational, electronic, nuclear spin,
etc.).

The HOMO-LUMO ΔE (the HOMO-LUMO gap) is an important property

for conjugated molecules.