ELECTRONIC

SPECTROSCOPY

SUBMITTED TO :- KANAD RAY SIR

SBMITTED BY :- AVINASH GUPTA
OUTLINE
ELECTRONIC SPECTROSCOPY
ABSORBANCE
DIPOLE STRENGTH
REFRENCES
Electronic Spectroscopy
Ultraviolet (UV) and visible (vis) spectroscopy:
This is the earliest method of molecular
spectroscopy.
A phenomenon of interaction of molecules with
UV and visible lights.
Absorption of photon results in electronic
transition of a molecule, and electrons are
promoted from ground state to higher electronic
states.
 UV and Visible Spectroscopy
In structure determination : UV-vis spectroscopy is
used to detect the presence of chromophores like
dienes, aromatics, polyenes, and conjugated ketones,
etc.
Also very useful in quantitative analysis of compounds
with chromophores.
Chiroptical spectroscopy- Optical rotary
dispersion/ORD and Circular dichroism/CD : the
difference in the refraction (ORD) or absorption (CD)
of left and right circularly polarized light is measured,
or absorptivity (CD) between left and right circularly
polarized light .
 Display of spectra

Horizontal scale (abscissa): all three methods

use wavelength, λ, in nm (nanometer) unit.
Vertical scale (ordinate):
UV-vis: absorbance, A, or molar absorptivity, ε.
CD: difference in molar absorptivity, Δε, or
molar ellipticity, [θ].
ORD: molar rotation, [φ].
Origin of electronic spectra
Absorptions of UV-vis light photons by
molecule results in electronic excitation of
molecule with chromophore.
The electronic transition involves
promotion of electron from a electronic
ground state to higher energy state,
usually from a molecular orbital called
HOMO to LUMO.
 Electronic transition
HOMO: Highest Occupied Molecular
Orbital
LUMO: Lowest Unoccupied Molecular
Orbital
Electronic transition usually originates
from valence electrons in a chromophore,
such as the nonbonding (n) or π electrons in
unsaturated functions.
Electronic transition
Can be assigned to different transition types
according to the molecular orbital involved,
such as π -> π* (in alkenes or benzene), n -
>π* (in keto group).
Due to their symmetry property in MO’s,
such transition can be allowed (high
intensity) or forbidden (low intensity).
Absorptions with high ε are allowed
transitions, and low ε absorptions are
forbidden transiton.
UV regions
The UV region is divided to two parts:
a. the near UV region: 190-400 nm.
b.The far or vacuum UV region: below
190 nm.
The far UV region has interference due to
absorption of oxygen, which must be
removed or flushed with nitrogen in the
spectrometer to obtain the spectra of
sample.
Measurement of Absorbance
The absorbance (A) or molar absorptivity
(ε) of an UV band is calculated according to
the Beer-Bouger-Lambert Law:
I0 : the intensity of incident light

I : the intensity of transmitted light

l : the path length in cm
c : the concentration in mol L-1
k : the absorption coefficient
ε : the molar extinction coefficient or molar
absorptivity in cm2 mol-1 or L mol-1 cm-1.
Absorbance
The relationship between k and ε is
Since absorbance A = , and A is the
actual quantity measured, the following
eqn. relates A with ε:
For i absorbing species :
The actual quantity measured is the relative
intensities of the light beam transmitted by
a reference cell containing pure solvent and
an identical cell containing sample solution.
Absorbance
Electronic transition
Electronic transition (UV) measure the
probability and energy of exciting a molecule
from G.S. to E.S. (or promoting electron from
HOMO to LUMO).
For each energy state both singlet (S) and
triplet (T) states are possible. In singlet state
the spins of electron pair are antiparallel; if the
spins are parallel, three states are possible and
are jointly called triplet state.
M = 2S + 1 M: multiplicity
 S: total spin
Electronic transitions
Selection rules: allow S→S, and T→T
processes but not S→T and T→S. Ground
states are usually singlets; thus most
excitations are to singlet excited states, like
S0→S1, S0→S2, …
Triplet states are usually formed by
intersystem crossing from an excited singlet
state, such as S1, rather than by direct
excitation from the S0 ground state.
 Electronic transitions
The electronically excited states may decay
unimolecularly back to the ground state by
photophysically emitting energy of fluorescence (from
an excited singlet state) or of phosphorescence (from an
excited triplet state).
Alternatively, it might decay photochemically to a
different ground state of different structure. One can
thus measure the absorption and emission from
molecules.
The λ of an absorption band correspond to the
max
excitation energy, and εmax to the intensity of transition, a
measure of the probability of promoting an electron,
given the excitation energy.
Electronic transitions

Intersystem crossing

Electronic activation and decay mode of a chromophore.

Classification of Electronic
Transitions
The wavelength of an electronic transition
depends on the energy difference between
the G.S. and the E.S. It is a useful
approximation to consider the λ of to be
determined by the ΔE of MO originally
occupied by the e’s at G.S. and the higher
excited MO in E.S.
The order: σ ->π ->n->π* ->σ*
Different type of UV transitions
 Terms describing UV absorptions
1.  Chromophores: functional groups that give
electronic transitions.
2.  Auxochromes: substituents with unshared pair e's
like OH, NH, SH ..., when attached to π chromophore
they generally move the absorption max. to longer λ.
3. Bathochromic shift: shift to longer λ, also called red
shift.
4. Hysochromic shift: shift to shorter λ, also called blue
shift.
5. Hyperchromism: increase in ε of a band.
6. Hypochromism: decrease in ε of a band.
Allowed and Forbidden transitions
Forbidden transition: The n→π* transition of satd.
ketones, where a carbonyl n electron is promoted
to an orthogonal π* orbital (n⊥π*); there is no
orbital overlap for such 90° movement of charge
and the transition moment is zero.
Allowed transition: For π→π* transition in double
bond, the symmetry of initial and final states are
the same and a large transition moment occurs to
give high intensity of the band.
Allowed and Forbidden transitions
Forbidden transition: The n→π* transition
of keto group is still observable with low
intensity, this is due to the vibronic states in
the transition. Symmetry of orbital changed
by C=O vibration that allow some overlap
of orbital and the transition to occur.
Absorption Intensity
Shape of electronic absorption band arises
from various vibronic sublevels. The band
intensity is described by εmax in UV. This
quantity can not be calculated theoretically,
but can be calculated by the wave-length
weighted area under the absorption band.
In UV curve it is called dipole strength D:

in erg cm3, (range 10-34 ～ 10-38)

Dipole strength
Dipole strength represents electronic
transition probability of the absorption
band.
As electron is promoted from low to high
E. states, a momentary electric dipole is
generated, called the electric transition
dipole moment μ, which is related to D by:
D is a dot product of μ.
.
Dipole strength
The following relations calculate D in
terms of Δλ (the bandwidth at εmax/2), εmax,
and λmax:
REFRENCES
GOOGLE
YOUTUBE
BOOKS, etc
Thank you for your
gracious presence
The end