Molecular Spectros
Molecular Spectros
Spectroscopy
(Electronic Spectroscopy)
(Optical properties)
Dr. Mohan Singh Mehata
(JSPS & CAS Fellow)
Molecular Vibrations
and
IR Spectroscopy
Spectroscopy
It is the branch of science that deals with the
Nobel Prizes
Nobel Prizes awarded in spectroscopy. These Prizes exemplify both experimental and theoretical contributions to
the growth of spectroscopic investigations as well as the development and discoveries related to spectroscopy.
Symmetrical
stretching
Asymmetrical
stretching
Scissoring
Rocking
Wagging
Twisting
Electromagnetic Radiation
Electromagnetic Radiation
Violet
400 - 420 nm
Yellow
570 - 585 nm
Indigo
420 - 440 nm
Orange
585 - 620 nm
Blue
440 - 490 nm
Red
620 - 780 nm
Green
490 - 570 nm
Principles of
Spectroscopy
Principles of Spectroscopy
The
principle
is
based
on
the
measurement of spectrum of a sample
containing atoms / molecules.
Principles of Spectroscopy
1. Absorption Spectroscopy:
Principles of Spectroscopy
2. Emission Spectroscopy:
An analytical technique
in which
emission (of a particle or radiation) is
dispersed according to some property
of the emission & the amount of
dispersion is measured.
I0
(powerin)
T = I/I0
I
(powerout)
A = bc
Where the absorbance A has no units, since A = log 10 I0 / I
is the molar absorbtivity with units of L mol -1 cm-1
b is the path length of the sample in cm
c is the concentration of the compound in solution, expressed in mol L -1 (or M, molarity)
transitions
can
Chromophore
The part of a molecule responsible for
imparting color, are called as chromospheres.
OR
The functional groups containing multiple
bonds capable of absorbing radiations above
200 nm due to n * & * transitions.
e.g. NO2, N=O, C=O, C=N, CN, C=C, C=S, etc
Auxochrome
The functional groups attached to a chromophore
which modifies the ability of the chromophore to
absorb light , altering the wavelength or intensity of
absorption.
OR
The functional group with non-bonding electrons
that does not absorb radiation in near UV region
but when attached to a chromophore alters the
wavelength & intensity of absorption.
Auxochrome
e.g. Benzene max = 255 nm
OH
OH
Alkaline
OH
medium
p-nitrophenol
max = 255 nm max = 265 nm
NH2
NH3 Cl
Acidic
medium
Aniline
max = 280 nm
max = 265 nm
CH3
Pyridine
2methylpyridine
max = 257 nm
max = 260
nm
Naphthalene
= 19000
2-methyl naphthalene
= 10250
Absorbance ( A )
Hyperchromic shift
Red
shift
Blue
shift
Hypochromic shift
max
Wavelength ( )
Principle
The UV radiation region extends from 10 nm
Instrumentation
Components of UV-Visible spectrophotometer
Source
Matchedquartzcuvettes
Sampleinsolutionatca.105M.
SystemprotectsPMtubefrom
straylight
D2lampUV
TungstenlampVis
DoubleBeammakesita
differencetechnique
Twophotomultiplier
inputs,differential
voltagedrivesamplifier.
LIGHT SOURCES
Wavelength Selectors
Wavelength selectors output a limited, narrow,
B. Monochromators
Wavelength selector that can continuously
scan a broad range of wavelengths.
Used in most scanning spectrometers
including UV, visible, and IR instruments.
PRISM TYPE
GRATING TYPE
Refractive type
Reflective type
Diffraction type
Transmission
SUMMARY
Types of source, sample holder and detector
SOURCE
SAMPLE
HOLDER
DETECTOR
Ultraviolet
Deuterium lamp
Quartz/Fused
silica
Phototube, PM
tube, diode array
Visible
Tungsten lamp
Glass/Quartz
Phototube, PM
tube, diode array
Emission
Fluorescence and phosphoresence
Jablonski Diagram
Jablonski Diagram
ESIPT
Ground State
Ionized species
Energy Transfer
Chromophore II
Ground State
Ground State
Chromophore II
FranckCondon principle
which states that an electronic transition takes place so rapidly that a vibrating
molecule does not change its internuclear distance appreciable during the transition
Examples
(molecular systems)
Lifetime
The lifetime of the excited state is defined by the average time the molecule spends in the excited
state prior to return to the ground state.
The lifetime of the fluorophore in the absence of nonradiative, processes is called the intrinsic
or natural lifetime, and is given by
In principle, the natural lifetime n can be calculated from the absorption spectra, extinction
coefficient, and emission spectra of fluorophores.
where F() is the emission spectrum plotted on the
wavenumber (cm1) scale, () is the absorption spectrum,
and n is the refractive index of the medium. The integrals
are calculated over the S0-S1 absorption and emission
spectra.
Kashas Rule:
Emission Spectra Are Typically Independent of the Excitation Wavelength.
Samples
A
l
Polymer film
ITO
Quartz
plate
C8H17
C8H17
N
O
Al
N
(n = 60, m = 40)
O
N
O
S
CONCLUSIONS
6-Hydroxyquinoline in benzene emits normal fluorescence around
357 nm.
In the presence of acetic acid (HOAc), it exhibits two more bands
at ~419 nm and a large Stokes shifted one at ~583 nm with
decreased intensity of the normal fluorescence.
It appears to form (1:1) and (1:2) complexes- (1:2) 6-HQ/HOAc
undergoes an excited state proton rearrangement (via HOAc wire)
resulting in keto tautomer (emitting at ~583 nm).
This appears to be in line with recent findings where ammonia
wires facilitate proton/hydrogen translocation (Science, 302, 1736,
2003). However, (1:1) 6-HQ/HOAc exhibits intermediate emission
(~419 nm) presumably due to ESIPT
Stark Effect
Electric field modulation spectroscopy
(Stark Spectroscopy)