Experiment 9

Laser Raman Spectroscopy

I. Introduction
When light encounters molecules, a small fraction of the incident radiation is scattered
off. The predominant mode of scattering is the elastic scattering in which the scattered and
incident photons are of the same energy (frequency). This elastic scattering is called
“Rayleigh scattering” and is responsible for the blue color of the sky because it increases
with the fourth power of the light frequency and is more effective at shorter wavelengths.
It is also possible for the incident photons to interact with the molecules in such a way
that energy is either gained or lost so that the scattered photons are shifted in energy
(frequency). Such inelastic scattering is called “Raman scattering,” which was named after
the Indian physicist C. V. Raman who discovered the effect in 1928. The Raman scattering
intensity is only 10-8 to 10-12 times that of the incident light, and is much weaker than the
Rayleigh scattering. Yet, the first observation of the effect was carried out by using filtered
sunlight, prism spectroscopes and visual detection!
A simplified energy diagram involving the concept of “virtual” states is given in Fig.1. A
virtual state is not necessarily a “real” stationary state (eigenstates) of the molecule and only
exists due to perturbation of the external EM wave during the course of photon-molecule
interaction. If the virtual level coincides with one of the molecular eigenstates, we call this
the resonance Raman effect. The energy of the scattered photon is less than the incident
photon for the Stokes line and the energy of the scattered photon is more than the incident
photon for the anti-Stokes line. In the vibrational Raman effect the energy increase or
decrease from the excitation is related to the vibrational energy spacing in the ground
electronic state of the molecule. Therefore, the Stokes and anti-Stokes lines are equally
displaced from the Rayleigh line. (see the schematic Raman spectrum shown in Fig. 1) Note
that the anti-Stokes line is much less intense than the Stokes line. This occurs because only
molecules that are vibrationally excited prior to irradiation can give rise to the anti-Stokes
line.
Raman Spectroscopy is based on the Raman scattering effect. Infrared (IR) and Raman
spectroscopy both measure the vibrational energies of molecules, but the two methods rely
only different selection rules. For a vibration to be IR active, the dipole moment of the
molecule must change with the vibrational motion. Therefore, the symmetric stretch in
52
carbon dioxide is not IR active because there is no change in the dipole moment. The
asymmetric stretch is IR active due to a change in dipole moment. For a vibration to be
Raman active, the polarizability of the molecule must change with the vibrational motion.
Therefore, the symmetric stretch in carbon dioxide is Raman active because the polarizability
of the molecule changes.

Figure 1. Schematic diagram showing energy levels and transition frequencies involved in Raman
spectroscopy. The thick upward arrows represent the excitation photons and the thin downward
arrows represent the scattered photons.

Raman and IR spectroscopy are the most important vibrational spectroscopic techniques
used by chemists. However, Raman spectroscopy has several advantages over IR
spectroscopy. A fundamental difference between IR and Raman spectroscopy is that visible
light can be used as the excitation source in Raman spectroscopy, which allows the use of
standard glass for the sample cells. Other advantages of Raman spectroscopy include: easy to
apply to aqueous solutions, no special sample preparation required, and vibrations between
400 - 10 cm (Far IR) can be measured with the same instrument. The developments in
high-power lasers and sensitive multichannel detectors, such as the charge-coupled devices
53
(CCD), have revolutionized Raman spectroscopy for analytical applications. In recent years
more sensitive techniques, such as the resonance-enhanced Raman, surface-enhanced Raman,
and Raman microscopy, have brought Raman spectroscopy to a new era for applications in
material and biochemical sciences. It can be expected that Raman spectroscopy will continue
to be one of the most important chemical spectroscopic techniques in the years to come.

II. Theory
In the following, we will describe a simplified classical model for the vibrational Raman
effect. When an external electric field is applied to a molecule, the electrons and nuclei
respond by moving in opposite directions, causing a change in the charge distribution. The
external electric field therefore induces a dipole moment (polarization) in the molecule. As
long as the external field is not too strong, the induced polarization is linearly proportional to
the field strength, and is given by
Pind = α E (1)
where α is the molecular polarizability and PBindB is the induced dipole moment. Higher
order terms must be considered if the external filed is very large, e.g. in the case of very
intense laser field. For a molecule that does not have spherical symmetry, each component of
the induced dipole moment can depend on each component of the electric field, and Eq. (1)
must be replaced by the matrix form

 PX    xx  xy  xz  E x 
    
 PY     yx  yy  yz  EY  (2)
P    zy  zz  E Z 
 Z   zx

Where  ij is the polarizability tensor. When molecules encounter an electromagnetic wave,

the external electric field is a time-varying function, E t   E 0 cos2 0 t  . At high optical
frequencies (~1015 Hz), the nuclei cannot respond rapidly enough to follow the field but
polarization of the electron distribution can occur, which generates an oscillating dipole in
the molecule at the same frequency
Pind t   E 0 cos2 0 t  (3)
According to the classical electromagnetic theory, an oscillating dipole will radiate
electromagnetic wave (scattered light) at its oscillating frequency. Thus, the induced
oscillating dipole can emit “scattered” photon at the same frequency in all directions (except
54
that parallel to the dipole). This process of re-emission of the induced oscillating dipole is
instantaneous and the intensity of the “scattered” light is proportional to the square of the
magnitude of the induced oscillating dipole.
The magnitude of the induced dipole moment is linearly proportional to polarizability,
which is a molecular property that depends on the nuclear and electron coordinates. When a
molecule vibrates its polarizability also changes. If only small vibrational amplitude is
considered, the dependence of polarizability on the vibrational normal coordinate can be
expanded as the Taylor series about the equilibrium configuration. If all terms beyond the
first-order term are neglected, then it becomes
  
   0     q n
n  q n  0

  0    n q n (4)
n

,where q n denotes the vibrational normal mode coordinates and  n is the polarizability
derivatives (rate of change in α with the nth vibrational coordinate). For small vibrational
amplitude the vibrational motion along the normal coordinates can be described as

q n t   q on cos 2 n t (5)

in which q on is the vibrational amplitude and n is the vibrational frequency of the nth mode.
Thus, the induce dipole moment becomes

Pind (t) =α(t)E(t)

 
   0    n q on cos 2 n t E 0 cos 2 0 t 
 n 
  0 E0 cos 2 0 t  E0  n qon cos 2 n t cos 2 o t 
n

EO
  0 E 0 cos 2 0 t 
2
   q [cos 2 (
n
n on 0   n )t   cos 2 ( o   n )t ] (6)

Since an oscillating dipole is a source of EM wave, the classical model predicts that the
 0 E0 cos 2 0 t ,
induced dipole can emit at several different frequencies. The first term,
shows that a scattered wave at the frequency of the incident light  0  is produced,
corresponding to the Rayleigh scattering. The cross terms in Eq.(6) represent scattered light

55
that can be generated at both higher  0   n  and lower  0   n  frequencies than the
incident photon. The incremental differences from the frequency of the incident radiation, 0 ,
are by the vibrational frequencies of the molecule, n . The  0   n  components are referred
to as the “Stokes” lines; and the  0   n  components are referred to as the "anti-Stokes"
lines. Eq.(6) also shows that the polarizability derivatives,  n   / qn 0 , must be
nonzero for the Raman scattering to be active. This gives rise to the important rule: For a
vibration to be Raman active, the polarizability of the molecule must change with the
vibrational motion. For example, homonuclear diatomic molecules do not have an infrared
absorption spectrum, because they have no dipole moment, but do have a Raman spectrum,
because stretching and contraction of the bond changes the interactions between electrons
and nuclei, thereby changing the molecular polarizability.
The ratio of the intensity of the Raman anti-Stokes and Stokes lines is predicted to be
4 h n
I A  0   n  kT
  e (7)
I S   0   n 

The pre-exponential term arises because the scattered light intensity increases with the fourth
power of the frequency. However,  0 is usually much greater than  n and therefore the
Boltzmann exponential factor is the dominant term in equation (7), which makes the
anti-Stokes features of the spectra much weaker than the corresponding Stokes lines.
Although the classical model correctly predicts the frequencies of the Raman lines, it
fails to give the correct intensities and a quantum mechanical treatment is required. The
quantum mechanical treatment predicts the same general results but more explicitly involves
the vibrational energy level and wave functions of the molecules. It is found that the intensity
of the Raman effect depends on the square of transition moment integral of the form
 

 1 * Pind 0 dq  (  1 *  ij0 dq) E i, j = x, y, z (8)

 

in which 1 and  0 are vibrational wavefunctions of the final and initial states, respectively,
 ij is anyone of the elements in the polarizability tensor, and the integral is evaluated in the
molecular coordinate system. The six elements of the polarizability tensor
 xx ,  yy ,  zz ,  xy ,  xz ,  yz all transform like the binary products of coordinates x2 , y2 , z2 , xy,
xz, and yz when the symmetry operations of the point group are applied. In order for the

56
corresponding integral to be nonzero and give an allowed Raman transition the direct product
1    ij   0  (9)
must contain the totally symmetric irreducible representation. This leads to a very simple rule
for the Raman activity: A fundamental vibrational transition will be Raman active if the
normal mode involved belongs to the same symmetry representation as one or more of the
Cartesian components of the polarizability tensor of the molecule. For example, x2 , y2 , and
z2 for the H2O molecule have A1 symmetry, while xy, xz, and yz have A2, B1, and B2
symmetry, respectively. Thus the three normal modes of H2O  1 (a1 ),  2 (a1 ), and  3 (b2 ), are
all Raman active.
Notice that if a molecule has a center of symmetry, then both  0 and  ij have g
symmetry and consequently 1 must also be of g symmetry. Thus, all Raman active
fundamental transitions have g symmetry if the molecule has a center of symmetry.
Correspondingly, all IR active fundamentals must have u symmetry since its transition dipole
moment has u symmetry. This leads to the rule of mutual exclusion, which states that no
fundamental mode of a molecule with a center of symmetry can be both IR and Raman active.
Comparison of IR and Raman band positions can be a simple but powerful tool in deducing
molecular geometry.
In this experiment we will study four molecules: C6H6 (benzene), CHCl3 and CDCl3
(chloroform and d-chloroform), and CS2 (carbon disulfide). Benzene is represented by the
D6h point group, and CHCl3 is represented by the C3v point group. The character tables
describing these two point groups are given in the Appendix I. The upper left corner of the
character table identifies the point group. The remainder of the first row of the character table
identifies the symmetry operations in the point group. The letters in the left column of the
character table represent the symmetry species that label the irreducible representations of the
group. The numbers in the table are the characters. To the right of the numbers in the table is
a set of six symbols, where x, y, and z are placed in the appropriate row of the table to show
how the symmetry operations of the point group affect these axes. The Rx, Ry, and Rz are
placed in the appropriate row of the table to show how the symmetry operations of the point
group affect rotation about these axes. The far right portion of the character table shows how
squares and binary products of coordinates are affected by the symmetry operations of the
point group.

57
 Raman Depolarization Ratio
The Raman scattered light is polarized even when unpolarized light, e.g. sun light or
mercury arc lamp, is used as the excitation. The polarization state of the Raman scattered
light depends on the nature of the vibrations involved. When the incident light is linearly
polarized, as in this experiment, the intensity of light scattered with polarizations parallel and
perpendicular to that of the incident light can easily be measured with polarizers. The
depolarization ratio of a Raman line is defined as
I
 (10)
I //
where I⊥ and I// are the intensities of scattered light with polarization perpendicular and
parallel to the polarization of the linearly polarized exciting light. The depolarization ratio is
related to the polarizability tensor  ij  components and is an important clue in the assignment
of a vibrational Raman spectrum because it depends on the symmetry of the vibrational mode.
From the theory of Raman effect, it is known that, for
linearly polarized incident light, 0    3 for totally symmetric vibrations and   34
4

for non-totally symmetric vibrations. Raman bands for which   34 are called depolarized,

and those with   34 are called polarized. Totally symmetric vibrations are those in which

the symmetry of the molecule does not change during the vibrational motion. For such
vibrations, ρ values near zero are observed for highly symmetric molecules such as CO2,
CCl4 and benzene. Thus, a measurement of the depolarization ratio can often distinguish
between totally symmetric and nonsymmetric vibrations. The measurement of depolarization
ratio will be used in this experiment to aid in assigning the frequency of the totally
symmetric vibrations.

58
III. Description of the Experimental Setup

Fig. 2 Schematic diagram for the laser Raman Spectrometer

Fig. 3 The laser Raman spectrometer

59
 In this experiment, you are going to operate a home-built laser Raman spectrometer to
measure Raman spectra of a few compounds. The challenge is to detect very faint Raman
scattered light that is very close in frequency to the extremely intense excitation light. A
schematic diagram of the laser Raman spectrometer is shown in Fig. 2 and a picture of laser
Raman spectrometer is given above. It consists of three major portions: an excitation laser,
beam steering and light collection optics, and a CCD (charge-coupled device) spectrometer.
The excitation laser is a solid-state diode laser emitting at about 638 nm. (to learn more
about diode lasers, click here [Link]
de.) The laser beam is directed by two aluminum mirrors (Al mirror) to strike on a Raman
notch filter at a small incident angle. The notch filter serves as a high-reflectivity mirror to
send the laser beam into a microscope objective (40X). It also serves as a filter to block the
much more intense Raleigh scattering from entering the detection system. The laser beam is
tightly focused into the sample cell (a standard NMR tube) by the microscope objective
(40X). The scattered light (Raleigh and Raman) is collected at 180° (backscattering) by the
same microscope objective and directed onto the Raman notch filter. This arrangement
ensures tight focusing of the laser and high collection efficiency of the scattered light. The
Raman notch filter allows the collected Raman scattered light to pass but rejects almost all
scattered light at the excitation wavelength. (see the transmission curve of the notch filter in
Appendix II) The transmitted light is then focused by an achromatic lens onto the entrance
aperture of a miniature CCD spectrometer for spectral analysis. A low-pass optical filter is
placed between the notch filter and the achromatic lens to further reduce the scattered light
level at the excitation wavelength. Light entering the spectrometer slit is dispersed by a
grating and then detected by a linear CCD array detector. The CCD detector has 2048 pixels,
which means a spectrum will contain 2048 data points. A schematic showing how the CCD
spectrometer works is given in Appendix II. Most optical components are mounted
with special devices (kinematic mirror mounts and translation stages) for easy
adjustment. The entire setup is assembled on an optical breadboard and is enclosed in a dark
acrylic glass box to reduce room-light interference.

60
Major Component List:
Here is a list of major components used in the laser Raman spectrometer. You are encouraged
to go to the manufacturer’s website to learn more about these components.
Model number and Important
Item Manufacturer
description specifications
Laser Coherent HNL225R λ=632.8 nm
[Link] Radius 632.8nm laser output power: 22.5 mW
/products/[Link]?834/ beam diameter0.7mm
Lasers
CCD Ocean Optics . HR2000 high resolution f/4, groove density=1200
spectrometer [Link] spectrometer l/mm, blaze λ=750 nm,
om/. slit=50 μm, λ
range=626 – 815 nm,
2048 pixels linear CCD
Notch filter Semrock . NF01-633U-25 See appendix
[Link] Stopline notch filter
/
Microscope Edmund . DIN achromatic 40X NA=0.65, working
objective [Link] spring-loaded distance=0.57 mm
s. com/. microscope objective
Achromatic Thorlabs . AC254-030-B Near IR D=25.4mm,F=30 mm,
lens [Link] achromatic doublets Near IR,Achromat,-B
Coated
Low-pass CVI . LPF-650 low-pass filter
optical filter [Link]
Aluminum BB1-E02 25.4mm Mirror,
Mirror Broadband 400-750nm

Note: the Raman notch filter is a very expensive (~NT$30,000) and delicate optics. Be
careful not to touch or scratch its surface.

IV. Experimental Procedures:

Precaution Notices: The laser used in the following procedures is a potentially hazardous
device. You should be aware of where the laser beam is shooting at all time. Never look
directly into the laser light source or at scattered laser light from any reflective surface
because it is particularly dangerous to your eyes.
61
 You have to carry out the following three steps in this experiment: (A) measure the
excitation laser wavelength, (B) optimize the optical alignment, and (C) measure Raman
spectra of benzene, CHClB3B, CDCl3, and CS2.
Before coming to the laboratory, you need to study the entire optical setup and
understand the function of each optical component. You also have to be familiar with the
Ocean Optics HR2000 high-resolution CCD spectrometer and its operating software
OOIBase32.(download operating instructions and software at .[Link]
It is similar to the spectrometer you used in P. Chem. Lab I to measure the visible spectrum
of the hydrogen atom, except that it has a narrower detection range and higher resolution.

(A) Measuring the excitation laser wavelength

The CCD spectrometer measures the wavelength of the collected scattered light. To
determine the Raman Stokes shift you need to know the excitation wavelength. Follow the
optimization procedure described in (B) up to step (4). Then, place a white card in the laser
beam path between the two Al mirrors and let the laser beam strike on the card such that
some scattered laser light can enter the spectrometer without going through the notch filter.
You should see a sharp peak that appears at about 638 nm. (You may have to move the white
card around to find a good spot!) Take a spectrum of the excitation laser and save it on the
disk.

(B) Optical alignment optimization

Although the laser Raman spectrometer has already been set up, you are required to
optimize its optical alignment in order to obtain good spectra. You will use a red fluorescent
dye (LDS750) to help the initial coarse alignment and then use the intense Raman signal of
benzene at 992 cm-1 (ring breathing mode) for the final optimization purpose. Before you
start, keep in mind that your goal is to collect as much Raman scattered light as possible into
the CCD spectrometer while blocking as much Raleigh scattering and background stray light
as possible.

62
 Follow the procedures described below for the optimization procedure.
(1) Open the lid of the acrylic glass box that encloses the laser Raman spectrometer.
(2) Power on the computer. Make sure the USB cable of the CCD spectrometer is properly
connected to the computer. Run the spectrometer software by clicking the “OOIBase 32”
icon. Make sure the software is properly running. (You should see a room light spectrum
displayed on the software window. If not, consult your TA) Play with the spectrometer
settings (axis scale settings, integration time, average, etc.) to get yourself familiar with the
system.
(3) Place a beam block about 5 cm from the laser output port. Switch on the diode laser
(Follow the turn-on procedure described in the operator’s manual). A red laser beam
should emit immediately from the laser and strikes on the beam block.
(4) Remove the beam block and use a white card to track the laser beam to see if it follows
roughly the beam path depicted in Fig. 2. (Caution: Do not touch or scratch any optics
with the white card! All optical elements used in this experiment are very expensive and
delicate!) If the laser beam path is far from expected, consult your TA for help.
(5)Place a white card at about 5 cm beyond the microscope objective. The expanded beam
profile projected on the white card should look symmetric and undistorted. If not, slowly
adjust the notch filter and the objective until the expanded beam profile projected on the
white card looks symmetric and undistorted. (this means the beam passes through the
optical axis of the objective)
(6) Place a cell containing neat benzene liquid in the cell holder.
(7) Set the integration time of the CCD spectrometer to 300 msec. If all previous steps have
been done correctly, then you should see a Raman peak at 992 cm-1 right away. (Note: the
CCD spectrometer measures the scattered light wavelength, not the Raman Stokes shift.
You have to calculate the corresponding wavelength to find this peak)
(8) Slowly adjust the position of the achromatic lens and the cell holder to maximize the
Raman signal for the 992 cm -1peak. This completes the optimization procedure
(9) Record a Raman spectrum of benzene and save it on the disk. You may have to play with
the software settings (integration time, average, etc.) in order to obtain a good (high S/N)
spectrum. Similar to the exposure time in your digital camera, the integration time
determines how long the CCD detector is exposed to the incoming light. A long integration

63
 time helps you to pick up weak signal and smooth out some electrical and stray light noise.
However, each pixel has a limited capacity for holding electrons, called well depth, and
thus a very long integration time may lead to overflow. To improve the quality of the
spectrum, you can increase the number of averaging. For example, if you set integration
time=5000 ms and average=10, the spectrometer will give an averaged spectrum of 10
continuously recorded spectra each integrated for 5 seconds. In this case, it should take
about 50 seconds to complete the acquisition.
(10) Remove the cell from the holder. Record a background spectrum using the same settings
used to acquire the benzene spectrum. The background spectrum will be subtracted to
remove some systematic noise and the unwanted leak-through Rayleigh scattered light.

(C) Measuring Raman spectra of other systems

You are required to measure the following compounds in this experiment: benzene,
CHCl3, CDCl3, and CS2. If you are interested, there are a few other compounds available in
the lab for your curiosity.

(1)Make sure the spectrometer has been optimized. Place a cell containing the sample you
want to measure in the cell holder. Adjust the spectrometer settings (integration time,
average, etc.) for obtaining good (high signal-to-noise ratio, S/N) spectra.. 1 Record a
Raman spectrum and save it on the disk.
(2)Remove the cell from the holder. Record a background spectrum using the same
spectrometer settings used in the previous step and save it on the disk. The background
spectrum will be subtracted to remove some systematic noise and the unwanted
leak-through Rayleigh scattered light.
(3) Repeat steps 1-2 for each compound. Minor adjustment may be necessary between
measurements of different samples.

1
Similar to the exposure time in your digital camera, the integration time determines how long the CCD detector is
exposed to the incoming light. A long integration time helps you to pick up weak signal and smooth out some electrical
and stray light noise. However, each pixel has a limited capacity for holding electrons, called well depth, and thus a very
long integration time may lead to overflow. The OOIBase32 program allows you to average a number of continuously
taken spectra to improve the S/N ratio. For instance, if you set integration time=3000 ms and average=10, the
spectrometer will give an average result of 10 continuously recorded spectra each integrated for 3 seconds. In this case, it
should take about 30 seconds to complete the acquisition.

64
 (D) Measuring Raman depolarization ratio
Use a Polaroid film polarizer. 2 to measure Raman spectra of parallel and perpendicular
polarizations with respect to the incident laser polarization. Place the polarizer right in front
of the low-pass filter (see Fig. 3) with a spring clip holder. The arrow mark on the polarizer
tells the axis of polarization. Look at the scattered light off the Al mirror through the
polarizer to determine the laser polarization. Record two Raman spectra: one with the
polarizer axis parallel to the laser polarization, another with the polarizer axis perpendicular
to the laser polarization. Because the Polaroid film polarizer works by absorption, all spectra
including the background have to be recorded with the polarizer in place. Repeat this
procedure for all samples, i.e. benzene, chloroform, d-chloroform, and carbon disulfide.

V. Data Analyses and Questions:

Use a spreadsheet program (for example, the Microsoft Excel) to subtract the background
spectrum from the raw spectrum. The spectra you obtained from the spectrometer are given
in wavelength (nm). It is usually more convenient to present Raman spectra with Stoke shift
in cm-1 . The Stoke shift in cm can be calculated using the following relation:
1 1
~RS (cm 1 )  
ex (cm)  scatter (cm)
,where  ex is the wavelength of the excitation laser and  scattered is the wavelength of
scattered photon. Use a spreadsheet program to convert wavelength to Stoke shift in
cm -1. Determine the Stoke shift (in cm-1 ) of each peak observed. (Note: you have to
show all spectra in your lab
report.)

Benzene
There are totally 3×12-6=30 normal vibrational modes in benzene. Group theory can
be used to predict their symmetries. Among the 30 modes, only 12 of them are Raman
active: 2 a1g, 2 e1g and 8 e2g modes. Since the e1g and e2g modes are doubly degenerate,
only 7 fundamental frequencies can be observed in the Raman spectrum.
(a) Find 7 strongest peaks in your benzene spectrum that correspond to the expected 7
Raman fundamental lines.
2
The Polaroid film polarizer is made from a long chain polymer (polyvinyl alcohol, PVA) with an iodine doping.
Stretching of the sheet during manufacture ensures that the PVA chains are aligned in one particular direction. Electron
from the iodine dopant are able to travel along the chain, ensuring that light polarized parallel to the chain is absorbed by
the sheet; light polarized perpendicular to the chain is transmitted.
(b)Find an IR absorption spectrum of benzene in the literature (or in your organic
chemistry textbook). Does any of the benzene Raman frequencies you observed
appear in the IR spectrum? Explain your finding.
(c) Use the measured depolarization ratios to identify the two a1 peaks.

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Chloroform and d-Chloroform
There are totally 3×5-6=9 normal vibrational modes in chloroform and
d-chloroform. Group theory predicts that there are 3 a1 and 6 e vibrational modes. The
modes of e symmetry are doubly degenerate, so only 6 fundamental frequencies can
be observed. Appendix I shows a schematic of the displacement vectors of each
normal vibrational mode in CHCl3. These are obtained with a standard procedure
called “normal mode analysis”, which involves solving the classical equations of
motion of all atoms with calculated or hypothesized force constants. The six modes
have been designated as: ν1(a1) C-H stretch, ν2(a1) symmetric C-Cl stretch, ν3(a1)
symmetric C-Cl bend, ν4(e) C-H bend, ν5(e) C-Cl stretch, and ν6 (e) C-Cl bend. (see
Appendix I). Carry out the following analyses and make a complete vibrational
assignment of the Raman spectra of chloroform based on ~  k /   2 and the
1

depolarization ratio. Do not simply use the finger print frequencies you memorized in
organic chemistry!
(a) Which normal modes of chloroform are Raman active?
(b)How many fundamental Raman Stoke lines (peaks) do you expect to observe? Is it
consistent with your observation? (note: ignore those very weak lines that are due to
combination and overtone bands)
(c)Use the measured depolarization ratio to identify the three a1 peaks in CHCl3 and
CDCl3 spectra. Assign each of these three a1 peaks to the fundamental a particular
mode. (Hint: use ~  (k / u ) 2 and the fact that chlorine is much heavier than
1

hydrogen and that force constants of bending modes are usually smaller than
stretching modes!)
(d) Compare the CHCl3 and CDCl3 spectra. It is clear that two of the high-frequency
peaks shift significantly toward lower frequency due to the substitution of hydrogen
with deuterium. This is a good example of the isotope effect of vibrational
frequency, which can give you additional clues. Given the highest frequency peak
position in CHCl3 (you should have made an assignment in (c) for this peak),
calculate the frequency of the corresponding mode in CDCl3 assuming a
pseudo-diatomic simple harmonic oscillator model. Compare the calculated and
observed isotope frequency ratio, i.e.( (~H /~D ) calc vs. (~H /~D ) obs . Is your result
consistent with your assignment in (c)?
(e) Another peak in CHCl3 and CDCl3 spectra also show a similar isotope effect. Make
an assignment to this peak based on the isotope effect and the depolarization ratio.
Explain why other vibrations do not show a significant isotope effect as the two
modes you assigned in (d) and (e).
(f) Now, there remain two unassigned peaks. Make an assignment to these two bands.
(Hint: use ~  (k / u ) 2 and the fact that force constants of bending modes are usually
1

smaller than stretching modes!) This completes the vibrational assignment of the
chloroform Raman spectrum.
(g) Find an IR absorption spectrum of CHCl3 in the literature. Does any of the CHCl3
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 frequency you observed in the Raman spectrum appear in the IR spectrum?
Explain your finding.

Carbon disulfide
CS2 is a linear tri-atomic molecule, which should have 3×3-5=4 normal modes.
The bending mode is doubly degenerate, so there are only three fundamental
frequencies that can be observed. They are usually designated as: ν1 (symmetric
stretch), ν2 (bend), and ν3 (asymmetric stretch).
(a) Which normal modes of carbon disulfide are Raman active? Which are IR active?
(b) Are the observed CS2 Raman spectrum and the depolarization ratio consistent with
the above prediction? (Note: ignore the small at about 800 cm-1 which is due to the
overtone of the bending mode)
(c) Find an IR absorption spectrum of CS2 in the literature. Does any of the CS2
Raman frequency you observed appear in the IR spectrum? Explain your finding.

※本教學實驗由教育部 ”提升大學基礎教育計劃”補助，鄭博元教授設計，賴思學先生(清大
化學 2005 級)協助建立。

References:
1. Experiments in Physical Chemistry, C. W. Garland, J. W. Nibler, D. P. Shoemaker, 7 th edition
(McGraw-Hill Science, 2002).
2. Spectra of Atoms and Molecules, P. F. Bernath (Oxford University Press, 1995).
3. Infrared and Raman Spectra of Polyatomic Molecules, G. Herzberg (1945).

APPENDIX I:
A schematic diagram of the displacement vectors in normal modes of CHCl3 is shown below.
Note that only one component of each degenerate mode is given.

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APPENDIX II:
Transmission curves of the Raman notch filter (NF01-633U-25)

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