In the name of Allah, The most gracious, The most merciful

Electronic
Transition
AYESHA YOUSAF
SHAISTA SHAUKAT
FAREEHA MARRIAM
SANA SHOUKAT
Electronic  When the molecule absorbs ultraviolet
or visible light, its electrons get promoted
Transition: from the ground state to the higher
energy state. This process is called
electronic transition.
 In ground state, spin of electrons in each molecular orbital
are paired
 In higher state, there are two types:
1. Excited singlet state
2. Excited triplet state
Excited singlet state

 If the spin of electrons in the higher state is paired, then it is

called excited singlet state.
 It is always higher in energy than excited triplet state.
 It is less stable than excited triplet state.
 Normally absorption of ultraviolet or visible light results in
singlet ground state to excited singlet state.
Excited triplet state

 If the spin of electrons in the higher state is parallel, then it

is called excited triplet state.
 It is always lower in energy than excited singlet state.
 It is more stable than excited singlet state.
 An excited singlet states converted to excited triplet state
with emission of energy as light.
 The transition from ground singlet state to excited triplet
state is symmetry forbidden.
FIGURE: ELECTRONIC TRANSITION
STATE
  The higher energy states are designated
as high energy molecular orbitals & also
called anti-bonding orbitals.
 The highly probable transition due to

Anti- absorption of quantized energy involves

the promotion of one electron from the

bonding highest occupied molecular orbitals

(HOMO) to the lowest available un-

orbitals filled molecular orbitals (LUMO).

 Electronic transitions
 According to the molecular orbital theory when a molecule
is excited by the absorption of energy (UV or visible light),
its electrons are promoted from a bonding to an anti-
bonding orbital.
 There are following types of electronic transition takes
place in UV and visible region:
1) s ® s* transitions
2) n ® s* transitions
3) n ® p* transitions
4) p® p* transitions
5) p® s* transitions
 Vacuum UV or Far UV
(Important in (λ <190 nm )
organic chemist)
UV/VIS
The energy required for various transitions obey the following
order:
s ® s* > n ® s* > p® p* > n ® p*
 s ® s* Transitions
 Transitions in which a s bonding electron is excited to an antibonding s *
orbital are called s ® s* transitions.
 It is high energy process since s bonds are in general very strong. The
organic compounds in which all the valence shell electrons are involved in
the formation of sigma bond do not show absorption in the ultra-violet
region, i.e.,180-400nm.
 For saturated hydrocarbons, like methane propane etc (which has only C-H
bonds and can only undergo s ® s* transitions) shows an absorbance
maximum at 150nm. Absorption maxima due to s ® s* transitions

 These wavelengths are lesser than 200 nm and fall in the vacuum UV
region.
Various
transition
involved in
electronic
spectroscopy
 n ® s* Transitions
 Saturated compounds containing one hetro-atom atoms with
lone pairs (non-bonding electrons) are capable of n ® s *
transitions.
 Compounds undergoing this type of transitions are saturated
halides, alcohols, ethers, aldehydes, ketones, amines etc need
less energy than s ® s * transitions.
 Water absorbs at 167nm, methyl alcohol at 174nm and methyl
chloride absorbs at 169nm.
 In saturated alkyl halides, the energy required for such a
transition decreases with the increase in the size of the halogen
atom (or decrease in the electro negativity of the atom)
 Comparison btw CH3Cl and
CH3I
Due to greater electro negativity of chlorine atom, the n
electrons on chlorine atom are comparatively difficult to
excite. The absorption maximum for methyl chloride is
172-175nm whereas that for methyl iodide is 258nm as n
electrons on iodine atom are loosely bound. Since this
transition is more probable in case of methyl iodide, its
molar extinction coefficient is higher compared to
methyl chloride.
Molar extinction coefficient (ε)
 The term molar extinction coefficient (ε) is a measure of how
strongly a chemical species or substance absorbs light at a
particular wavelength.
 It is an intrinsic property of chemical species that is dependent
upon their chemical composition and structure. The SI units of
ε are m2/mol, but in practice they are usually taken as M-1cm-1.
The molar extinction coefficient is frequently used in
spectroscopy to measure the concentration of a chemical in
solution.
 p ® p* Transitions
 This type occurs in the unsaturated centers of the
molecule i.e., in compounds containing double or
triple bonds & also in aromatic.
 These transitions require smaller energy hence it
occur at longer wavelength.
 These are the transitions in which an electron in a p
electron is promoted to an antibonding p* orbital.
 For e.g., alkenes, alkynes, carbonyl compounds,
cyanides, azo compounds etc. show p® *p*
transitions.
 n ® p* Transitions
 These are the transitions in which an electron in a non-bonding
atomic orbital is promoted to an antibonding p* orbital.
 Compounds having double bonds between heteroatoms, e.g.,
C=O, C=S, and N=O.
 These transitions require least amounts of energy hence occur
at longer wavelength.
 For e.g. ,the >C=O group of saturated aldehydes or ketones
exhibit an absorption of low intensity at about 285 nm.
 High energy transition
 Absorption occurring at lower wavelength is usually intense.
 n ® s* (intense)
 p® p* (intense)

Low energy transition

 Absorption occurring at longer wavelength is usually weak.
 n ® p* (weak)
 Transition Probability
It is the probability or chances of
particular transition to occur.
  The transitions with values of extinction
coefficient more than 10,000 are usually
called allowed transition.
 This generally arise due to p® p*
Allowed transition.

Transitions  In 1,3-Butadiene, the absorption is 21ooo

at 217mµ is an example of allowed
transition.
 In this, the probability of transition is
high.
 The transition with value of absorption
coefficient generally less than 10,000 are
called forbidden transition.

Forbidden This arises due to n ® p* transition.

In carbonyl compounds, this transition
transition occurs at 300mµ
With coefficient value between 10-100.
In this, the probability of transition is low.
  The transition is related with the
geometries of the lower and the higher
energy molecular orbitals and on the
symmetry of the molecule as a whole.
Symmetry  Symmetrical molecules have more
Restrictions restrictions on their electronic transitions
than less symmetrical molecules.
in Electronic  Like benzene, it is more symmetrical, so
Transitions restrictions apply, and its electronic
absorption spectrum is simple than
asymmetrical.
 Following factors decide whether the
transition is allowed or forbidden:
 Geometry of MO in ground state
 Geometry of MO in excited state
 The orientation of electric dipole of the
incident light that might induce the
transition.

 The transition will be allowed if the above

three factors have an appropriate symmetry
relationship.
Electronic Transition
for Charge-Transfer
Complexes
INTRODUCTIO
N
In complexes formation, there
involves the transfer of electronic
charges from an electron rich
molecule to an electron deficient
molecule with molecular orbitals
of suitable energy and symmetry.
These complexes are called as
Charge transfer Complexes.
Example

LAN-Picric acid Charge

Transfer Complex:
This complex gives
brown color.
Donor: Picric Acid
Acceptor: LAN
 Charge Transfer Donors

Aniline NN-Dimethyl Anthracene

Aniline
 Charge Transfer Acceptors

Picric Acid Aluminum

TCNE
Chloride
 Electronic Transition for Charge Complexes

on

west

The λmax = 280 nm for Aniline & λmax = 300 nm for Tetracyanoethylene
but the complex of aniline with TCNE absorbs in Visible region at
λmax = 610 nm

Any Question!
Thanks!