Raman Effect
Raman Effect
Kanpur
NP-TEL
National Programme
on
Technology Enhance Learning
Course Title
Advanced Characterization Techniques
Lecture-07
by…
Prof. Krishanu Biswas&
Prof. N.P Gurao
Dept. Materials Science &Engineering
In this class today we are going to discuss about a very important spectroscopic techniques called
Raman spectroscopy.
And as you know Raman was an Indian and lot of in Curtin aspects are involved in relating this
spectroscopic technique so I will be able to do a little bit of justice to this in one-hour time but I
do not think it is possible to talk about the details of the spectroscopy in just a short span of time
because a lot of aided theories are needed to be covered in such a class but I am going to give
you some basic idea of the spectroscopic technique how it can be related to applications and
obviously some amount of instrumentations will be dealt with.
As you know the outline is like this obviously there will be some aspect of introduction going
back to history and some basic features and then I will talk about some basics of the Raman
spectroscopy where I will talk about theories and then some amount of scattering and vibrations
and finally some instrumentation for Raman spectroscopy and obviously you know during the
course of the lecture I am going to talk about some examples from the literature from some of
our own work.
But there is a distinct difference between IR and the Raman spectroscopy in fact IR spectroscopy
the band's arises from the change in the dipole more and other molecule but Raman’s bands arise
from a change of the polarizability not the change in the dipole moment remember so it is the
porosity price the ability change that makes the Raman’s so interesting so therefore the
symmetric molecule it will not work that is the most important problem in Raman spectroscopy.
In many cases transitions that are allowed amounts are forbidden in IR so there are techniques
these two techniques are basically complimentary to each other so you will see that we also a
comparable spectra from the Raman and from the IR to show you how this the techniques can be
used for Complementary so therefore as I said at the very basic aspect of the Raman spans
arising during measurements is the change in polarizability of the molecule that basically sets an
exclusion rule.
What is the exclusion rule it says if the molecule has a center of symmetry then no modes are is
active whatever is a IR and Raman so as you can look into his this slide you will it will be clear
to you for a molecule.
(Refer Slide Time: 03:36)
With a center of symmetry as I said no IR active tensions are Raman active or vice versa what is
it let us suppose this molecule which is Coo that is co 2 and you know it is Raman active but IR
active but on the other hand if the molecule has changed that means if this molecule is little bit of
you know center of symmetry chain little bit this side right side then it becomes Raman active on
the other hand if the molecule become fully central symmetric then no bands no none of these
techniques can apply.
That is what this Inelastic scattering means actually because Inelastic scattering was known or
even long back from Raleigh law dry less time but Inelastic scattering was not fully understood
so it was in the early part of the last century 20th century these things have started in 1928 CV
Raman and one of his students very last is a student's K.S. Krishna first time while working on
different solvents saw feeble fluorescence and it was reported.
And after within two years it was we have come so no intense our activity Raman was awarded
Nobel Prize to tell you that K.S. Krishnan this is the picture both of them are taken form
studyhelpline.net where you can get bio-data this is Raman’s picture and this is Krishnan just to
impress you up on that in those days when India was under British rule still there are scientists
were working on path-breaking research.
And it was only possible because of these two gentlemen who worked hard to put the things into
the world's perspective as per scientific content is concerned so and but you know Nobel Prize
was given to C.V. Raman, K.S. Krishnan obviously was a PhD student who work hard to prove
that so his contributions were null nowhere less so that is why I already show you and then 1961
laser came and on the maser actually after the Second World War and 1977 first time using laser
surface yeah enhance Raman scattering was discovered.
This is thanks to laser on a lead as possible to discover that and 1997 that is the big change
happened in the Raman spectroscopy another big change when single molecule shows surface
enhance among spectroscopy spectrum or scattering so therefore nowadays we can actually go
all the way to the single molecule and get Raman scattering and then prove it using Raman
spectroscopy technique.
So that is how it is actually possible as soon as you understand talking all this surface on
Raman’s spectroscopy and single molecules almost Raman’s spectroscopy another spectroscopy
is beyond the scope of this course so those of you who are really interested or maybe using this
technique extensively they can look at different books which I will show you even some of the
references while give me the lectures and then understand or try to understand maybe these are
very advanced topics not even part of the discourse.
Let us look into theory in detail that will tell you hi the Raman’s actually scattering happens and
how it can be utilized.
And some amount of photon with less frequency obviously will come out because some I want to
has been absorbed that is what is the nature of inelastic scattering you should know that and this
will lead to vibrations under these vibrations can lead to fluorescence and this source scatterings
and as is gained by the photon instead of loss so what happens you have a photon in and there is
a vibration.
And then photon absorbs this molecule exclaims of a photon so some photon goes out but you
know energy is gained by the photon in this way so there is no vibrations but there are two kinds
of scattering as you see in which one is energy is lost by the photon or other energy is gained by
the photon and both inelastic is scattering times they are called Stokes and Anti Stokes now there
is obviously dominant scattering process which is inelastic scattering.
So therefore inelastic scattering basically λ does not change the length of the vibration does not
change it can have random direction of emissions does not lead to fluorescence and there were
little energy loss so therefore it is not and this is what is the basically the scattering energy where
these are the different parameters the λ disturb when these energies energy ground state θ is the
energy at which it is scattering of angle.
So as we see I have seen that there are two kinds of scattering one is elastic other one is Stokes
anti-stokes which are basically known as inelastic scattering and they are ready to Raman so if I
consider E0 as my ground state for the molecule and this is the vertical axis the energy so
whenever certain infrared radiation is imposed on this molecule it will absorb and go to the high
energy band that is suppose the excited States and when it is comes backs it gave it the radiation
and that would detect it and that is what is the principle of IR spectroscopy.
Now, one can always think the glace scattering or elastic scattering in this way we have a higher
energy hν0 by which the molecule is goes to virtual excited States not the nearest excited state
and when similar amount of energy is released by the molecule it comes back to the ground state
that is what I have shown you in the last slide here exactly the same thing now in case of Stokes
suppose molecule is excited to the higher in the state of virtual state by h ν energy level and there
is some inelastic scattering happens some energy get lost.
So that it does not come back to the ground state at all that means it lost energy but the molecules
can come back by losing this energy hν 0 - hν1 to then excited States and vibration States the
above the ground state that is what is this one so if you see obviously you can see it confuse
easily when it comes back to the ground state another situation can happen an anti stroke scatter
what is that molecule can get excited to the hierarchy state previously virtual states okay.
And when it goes there it gets to these virtual states it gathered more energy maybe it can have h
ν 1 external g okay so that total energy of the molecule increased because it absorb another
photon other than hν0 and when it comes back to the ground States it just have external energy
which is also coming out hν + h2o this can also lead to fluorescence.
So therefore both at stop scattering anti scattering can lead to Roman that is what I am saying but
the catch is this the Raman’s effect comprises a very small fraction about 100 of those 7 of the
incident photon so that means we need to have very good probe to detect the small number of
photons which are actually undergoing this.
So that means one into verse seven photons is scattered in less physically so almost bulk of the
photons get scattered by inelastic and they can have we can have different kinds of Raman
spectroscopy depending on what kind of you know scattering is what kind of things are
happening like rotational States or vibration States or electronic states energy level.
But in case of IR halide optics must be used as we have seen they are very expensive can be
broken it can be water absorb also because they do not absorb the basically are then halides and
IR radiation and it is not possible to get a good data IR spectrum emitters are not usually
equipped with polar ideas on the other hand now inspectors meters are usually grouped with
polarizer’s.
How does the Raman spectra spectrum look like well this is what is shown you in dumps in the
picture.
So you can see these are the frequency differences - and these are the frequency different + for
the anti Stokes and this is a Ray lied so Rallied will be the highest peak because inelastic
scattering on the left of the ray lay but less wave numbers will be the strokes on the right side
will anti strokes by elastic scattering in inelastic scatterings where energy is lost energy is
gained.
So I can always write down this is the Hookes law force law basically m1 m2 / m1 + m2 double
derivative of space or the extension with respect to the time this is nothing but this + this sorry
this nothing but acceleration or deceleration this the mass this basically reduced mass you can
say and that will be related to be the K x1 + x2 so therefore I can write down this in terms of μ
dq/ dq2 q/ dt2 = K into q - this is q is extra displacement and this can be solved this where Vm μ
m basically = 1 /π √K/μ.
This is nothing but the frequency of vibrations so that is what is the you know whenever a
molecule is stretched or excited this is what will happen it will X private with this and this will
be d basically displacement can be related to the vibration this way cubes will accuse you the
cause of 2π through μm into T.
(Refer Slide Time: 22:09)
Now if once you look at it you know in different perspectives suppose this is the molecule which
is vibrating as you see last time and this is the probably change of distance vibration Q and we
are putting in certain radiations which is given by this equal to E= E0 cos of 2 π μ0 T so
therefore this will lead to an dipole moment induced dipole moment that committed to α into e α
is the paralyzed and E is this E0cos of this so for small amplitude of vibration the polarizability α
is linear function of q as you can see.
So therefore we can write down α = α 0 al dl α /dq into q and ignoring the high order terms so P
can be related to this way α 0 a 0 you can see you can plug in this one and a big equation and as
finally after solving all this equations which I have done here in the slide you can get inelastic
scattering it given by this and unless the scattering is given by this in the inelastic scattering part
you can always get μ 0 - μ Pm or μ 1 μ 0 + μ m so this is basically Stokes this is anti-stokes.
These two are the factors which are responsible for the Raman’s scattering so by just putting is
this is simple molecular structure and then one radiations we can always calculate the
polarization or induce dipole moment and you can see dipole moment can calculation can lead to
us this kind of mathematical theory so therefore if I want to give you some example let us
suppose for carbon dioxide here you have CC.
So finally again I put down this equations where the rally the Inelastic scattering and unless the
scattering events are both are given.
So more molecules per many molecules probably difference in the direction of the applied fields
tension of the applied fields like hh easier to distort along the bonds than partner to the bond so
plausibility is anisotropic variation of the Α with Direction is describe a possibility tensor a
tensor is another vector which can be used to detect to basically show a variation of α with the
direction now vibration is active it is if it has a changing probability any vibrations in the
molecule if you put in an aunty will be active Raman active if there is a change in the
polarizability α.
So the starting vibration going the electric field of the radiation at time T is induced due to
separation of charges as you at the beginning you put electric field it is separate some charges
and then this is called singly dipole moment which can be related to this P into α and we
remember α is basically the polarizability so we are talking about this change of α not change of
P which is required for Raman change of P is required for the iron please do not get confused to
the molecules dipole moment or the change in dipole moment because this is always case to be 0,
these molecules again I come back to see a stood CL 2 okay, so sorry I come back to this wrong I
come back to co2.
And this is what we can show this is a μ one so you can see Paula little is changing like this is μ
3 small not active but polarization dipole of moment is changing extensively, here dipole
movement does not get changed.
Because there is a lot of change of probability of the molecule they are all obtained from
municipal.
And E is the energy of that states and they this is basically exponential term conflicts of
Boltzmann’s. So this σ Thomas target is represented by a molecule for scattering that is what is
this scattering cross-section, how much is that area target area by molecule for scattering even
occurs?
So if I have to compare this with other techniques like UV IR flow sensor Ally Raman and other
surface enhanced Raman you can see the scattering cross section is very high very high means
not very high 10 to the -18 is pretty low but still it is high in case of UV and IR relay and Raman
is pretty low 10 to the - 26 - 29 that is the problem actually I want spectroscopy you need to have
a very good detector to detect this scattering turrets.
It is you can see that it is false and then does not grow like this but it comes back and I am
scattering angle collected by colleague collecting lens focusing lens analyzer then polarizations
gambler and then it goes to this in slits and then want to come across things in this part of this
monochromatic you have several important aspects one is the controller, second one is the
photon counter proton gain can be counted by PMT photo multiplier tube and then you have a
controller which you plot this display this data and I never display.
So that is what is the basically I think I have already discussed with you was monochromatic in
case of total emission spectroscopy, so the spectral gap is where the data are plotted.
Let us look at first a double monochromatic, so you can clearly see that these are these splitters
mirrors actually it falls comes and falls on a mirror I am sorry it falls on m1 then goes on to G 1
then again M 2 gets reflected finally it's comes out through this, so entrance and this from the
entrance and the exit there are only 1 M 1 2 m 5 there are 5 minutes and there are this splitters G
1 G 2 and they are all actually an indeed by this way you can actually get these monochromatic
radiations.
And otherwise you can do what you can do is this way you can have entrance then it passes to lot
of bands passes finally it goes to the subtractive dispersal and it falls on a three turret getting
assembly and then comes out well we will not discuss, so much detail but there are two types of
spectral gaps used one is a double monochromatic type one is typical monochrome and
depending on this has a better ability to collect data than this one.
And you can always use otherwise CCD cameras are charged coupled device where you can
actually pixel types in which you can detect radiations coming on each pixel.
Few invents of atoms on combination bands like few spectral of elapsed can be done you can
totally symmetric vibrations are observable Ramans in the cities are basically proposition the
concentration and the laser power this is the proportionality constant not α. Well as you have
seen that this is much simpler and cheaper than the spectroscopy it has experimentation is too
medicine is much less but the lower detection limit is the problem in case of Raman so
background flow sense can always propagate which you will see how to take care and more
suitable for vibration with bonds in low like chlorine carbon fluorine bonds.
Acknowledgement
Ministry of Human Resources & Development
Satyaki Roy
Co Co-ordinator, NPTEL IIT Kanpur
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