2-1

Spectroscopic Studies of HCl and DCl

* Butera, R.A., Waldeck, D.H and Wagner, E.P.
Revised January 2012
Introduction
High-resolution infrared spectroscopy is one of the most useful tools for investigating the
structure of small molecules. In this laboratory, you will practice some infrared techniques and
analyses for one of the canonical problems in spectroscopy, obtaining the bond length of a
diatomic molecule. You will learn about the careful use of glass vacuum lines to prepare gas
phase samples for analysis and the operation of a Fourier transform infrared spectrometer. In the
analysis you will review the quantum mechanics for a rotating-vibrating molecule and use the
data to determine some of the molecular characteristics of HCl and DCl.
Theory
Vibration-Rotation Spectra:
Photons in the infrared range of the electromagnetic spectrum have the correct energy to
excite molecular vibrational modes. Because of the selection rules for absorbing radiation,
vibrational excitation is usually accompanied by rotational excitation. For energy levels near the
bottom of the potential energy well of a diatomic molecule, the energies of the rotationalvibrational levels are given, in units of cm-1, by:
2

Ev , J

1
e v e X e v Bv J ( J 1) De,v J 2 ( J 1) 2
2
2

(1)

where the first and second terms account for the vibrational energy, and the third and fourth
terms account for the rotational energy. The fundamental vibrational frequency of the molecule
is e. The first anharmonic correction to the vibrational frequency is eXe. B is the rotational
constant for a given vibrational level, and De is the centrifugal distortion constant. The integers
and J are the vibrational and rotational quantum numbers respectively. They label the energy
level of the molecule. B may be obtained from the equilibrium geometry of the molecule using
the relationships:
1

(2)
Bv Be v
2

and
h
ma mb
(3)
Be (cm 1 )
; I e re2 ;
2
8 cI e
(ma mb )
Here Be is the equilibrium rotation constant, is the anharmonicity correction factor to the
rotational energy, Ie is the equilibrium moment of inertia, the reduced mass and ma and mb are
the masses of the two atoms that comprise the molecule. The vibrational frequency e is related
to the bond force constant ke by the expression:

ve

2c

1/ 2

ke

(4)

2-2

Figure 1: Anatomy of a vibration-rotation band showing rotational energy levels in their

respective upper and lower vibrational energy levels, along with some allowed transitions. The
spectral lines corresponding to these transitions are shown in the spectrum. Note the splitting
that arises from the H35Cl and H37Cl isotopic shifts.

2-3
The force constant ke is given by the second derivative of the bonds potential energy curve with
respect to its displacement, evaluated at the equilibrium internuclear distance re. The derivation
of these equations is discussed in most elementary physical chemistry texts.
Absorption of a photon can only occur when the photon energy is equal to the energy
difference between two energy levels of a molecule. A further restriction on the absorption is
that selection rules must be followed in the transition. For a diatomic molecule which is
modeled as a harmonic oscillator (with a dipole moment), the selection rules are = +1 and
J = 1. For an anharmonic molecule (that is all real molecules), the selection rule for is
not strictly followed, i.e., = +1, +2, . One of the things you will explore in this lab is how
strongly this selection rule ( = +1) holds for DCl.
Figure 1 illustrates the energy levels for the two lowest vibrational states of the molecule
and shows some of the transitions that are allowed between the sublevels. Also shown is a
hypothetical IR spectrum. What you should notice is that the spectrum is separated into two
branches, with a gap between them. The gap is where the infrared transitions would be if no
change in the J value occurred, i.e, J = 0. This region is referred to as the Q branch and only
involves a change ion the vibrational quantum number. The low frequency branch consists of
J = -1 transitions and is called the P branch. The high frequency branch consists of
J = +1 transitions and is called the R branch. Note that the quantum numbers for the lower
state in the transition are traditionally labeled as and J while those for the upper state are
labeled and J.
You will notice that as you count away from the center of the spectrum the intensity of
individual lines increases, goes through a maximum and then falls off in the wings. This pattern
arises from a combination of two effects, the population of molecules in a quantum state and the
number of quantum states at a particular energy. Within a band, the intensities are proportional
to the population of molecules in the ground vibrational-rotational level. The population in state
J is given approximately by the equation:
B J ( J 1)
(5)
N ( J ) N 0 (2 J 1) exp 0

kT

where k is Boltzmanns constant and must have the proper units so that the argument of the
exponential factor is unitless (you must convert kT to wavenumbers) and N0 is the population in
the state = 0, J = 0. The (2J + 1) factor is the degeneracy of the rotational energy level and
arises from the fact that 2J + 1 values of the m (orientational) quantum number are possible for
each value of J. The exponential factor is called a Boltzmann factor and gives the temperature
dependence of the distribution. (Here we have neglected the possibility that a few molecules will
be vibrationally excited.)
As in all quantitative work, using the correct units is vital to avoid extracting nonsense
from the spectra. In molecular spectroscopy, it is usually safest to convert everything to cgs
units. To make sure you know where to begin, you should decide on consistent units for e, Be,
Ie, re, De, and ke. The following constants and values may be helpful.
h = 6.626 10-27 erg s
k = 1.381 10-16 erg/K
1 cm-1 = 1.986 10-16 erg
mH = 1.007825 amu
mD = 2.0140 amu
35
Cl = 34.968852 amu
37
Cl = 36.965903 amu

=
=
=
=
=
=
=

6.6261 10-34 Js
1.38066 10-23 J/K
1.98630 10-34 J
1.672623 10-27 kg
3.3425 10-27 kg
5.803558 10-26 kg
6.135000 10-26 kg

2-4
The first step in determining the structure of a molecule is to obtain high quality spectra.
The following section of this handout will describe how you obtain the spectra of the
fundamental transitions for H35Cl, H37Cl, D35Cl, and D37Cl, and the first overtones of the
deuterated species.
Laboratory Procedure
The laboratory procedure has two main parts. In the first part you prepare the sample. In
the second part you record the IR spectrum.
Vacuum line and sample preparation
Both HCl and DCl can be prepared through a chemical reaction under vacuum. Although
youll be using D2SO4 to form DCl, sufficient amount hydrogen will be present to allow some
HCl to form.
D2SO4(l) + 2KCl(s) 2DCl(g) + K2SO4(s)

Before trying any of the procedures described here, you should read this entire section while
studying the diagram of the vacuum line in Figure 6. When in the laboratory, you should
visually examine the vacuum line and you should make sure that you understand the purpose of
each valve and the consequences of opening or closing each valve. A glass vacuum line is a very
fragile piece of equipment, which is handmade by a skilled glassblower. A sudden, or forced
movement can result in the fracture of a joint or tube, and the subsequent release of a large
amount of gaseous HCl. Therefore, when working on the vacuum line, every action must be
well planned, and every movement slow and deliberate.
HCL IS AN EXTREMELY TOXIC GAS, AND CAN CAUSE SEVERE RESPIRATORY
DAMAGE. YOU MUST BE WEARING LATEX GLOVES AND EYE PROTECTION
BEFORE PROCEEDING.

Figure 6: Vacuum line system.

2-5
Grease the cold trap joint (You only need about the amount equal to the size of a pea for this
large joint.) and install the cold trap by twisting it onto the joint.
ALWAYS USE TWO HANDS WHEN APPLYING A FORCE ON THE GLASS: ONE
FOR TWISTING, THE OTHER TO BRACE THE JOINT.

Place the dewar around the trap and adjust the support to hold the dewar.

Check to see that all three manifold valves are closed and that the valve to the trap is open.
The vacuum release valve, just above the rubber tube leading to the vacuum pump, should
also be closed.

Turn on the vacuum pump. Any time the pump is pumping a large volume of gas, it will
make a loud gurgling sound because it is working hard. When the volume is evacuated, the
pump will operate quietly. Therefore, any time you open a valve to evacuate a section of the
line and the pump works hard for more than a minute, you have left a valve open or you have
a leak. (In this latter case, you may also hear air hissing into the line.) If this occurs, you
should immediately close the valve you opened and find the leak.

Once the pump is operating quietly, open the vacuum pump cut off valve. Again, the pump
should make a loud gurgle initially, but run quietly after a few seconds. Also note that the
vacuum gauge should indicate a very low pressure (~10 millitorr). If the vacuum gauge
reading is high, youll need to check for leaks.

Attach the IR gas cell to the first valve on the manifold. Make sure that you do not touch the
cells windows. Open the manifold valve first and evacuate the tube leading to the cell. If the
vacuum is holding well, install a spring clamp on the ball and socket joint so that the cell
does not fall off of the manifold line. Next open cell valve and evacuate the cell. Again,
make sure there is a good vacuum. Note: the cell valve is special in that the body of the
valve is hollow and needs to be evacuated in order for it to work well. Look closely at the
valve barrel and you will see a small pin hole used to evacuate the valve body (Figure 7).
Line this hole up to the vacuum line first and evacuate the valve body. After it is evacuated,
you can turn the valve back on to the cell.
Pin hole to evacuate
the valve body

Figure 7: Valve barrel for IR cells.

Put on the face shield over your goggles and fill the dewar with liquid nitrogen.

2-6
NOTE THAT THE LIQUID N2 WILL BOIL WHEN IT HITS THE WARM DEWAR
AND TRAP, SO IT MUST BE FILLED SLOWLY OVER A FEW MINUTES. LIQUID
NITROGEN WILL INSTANTLY FREEZE YOUR SKIN IF YOU GET A SIGNIFICANT
AMOUNT ONTO YOUR HAND (A SIGNIFICANT AMOUNT IS ANY VOLUME
GREATER THAN A FEW DROPS). THIS FREEZING MAY CAUSE A VERY
PAINFUL BURN, SO BE CAREFUL.

Weigh out 3g of KCl and place it, along with the magnetic stirring bar, in the 2-neck reaction
flask. Be sure that you do not get any KCl on the flask joints. If you contaminate the
joints, you should remove the KCl before proceeding.

Insert a small magnetic stir bar.

Install the adapter onto the middle neck. Use enough grease to seal the joint (much less than
the size of a pea) and attach the retainer clamp.

Attach the reaction flask to the third manifold valve using the adapter. To make sure the
joint is lubricated, you should rotate it. Attach a spring clamp to the ball and socket joint.
Rotate the flask so that you can install the dropping funnel.

A glass dropping funnel will be used to add the D2SO4(l). Lubricate the bottom joint and
install it on the reaction flask using grease and the retainer clamp.

Close the valve on the dropping funnel and then open up the manifold valve and evacuate the
entire reaction flask. Make sure it is holding a good seal before continuing.

Slowly raise the plate supporting the magnetic stirrer until the stirrer is approximately 2 mm
underneath the reaction flask. When in position, hand-tighten the locking nut.

Turn on the stirrer and make sure the bar in the flask rotates then turn the stirrer off.

First make sure the stop cock at the bottom of the dropping funnel is closed (perpendicular to
the vial). Remove a vial of D2SO4 from the desiccator. Using a desposable pipette with great
care, withdraw approximately 5 ml of D2SO4 and put it into the dropping funnel. The D2SO4
is very toxic and difficult to work with, so make sure you have gloves on and you handle it
carefully.

D2SO4 IS CONCENTRATED SULFURIC ACID, AND IS BOTH DANGEROUS AND

VERY VISCOUS.

Put the stopper into the top of the funnel.

Place the vial of D2SO4 back into the desiccator.

You are now ready to start the reaction and let the gas product fill the vacuum line and the IR
cell. Before continuing make sure the vacuum line is holding a good vacuum by shutting the

2-7
vacuum pump cut off valve. The line pressure should not increase above 50 millitorr. While
you will see some increase in the pressure reading on the meter, it should be a slow increase.
If you think it is increasing too quickly, check for leaks and consult your TA.

Verify that the valves leading to the reaction flask and the IR cell are open and that the
vacuum pump cut off valve is closed.

Turn on the magnetic stirrer and then slowly open the valve at the bottom of the dropping
funnel and allow a couple of drops of D2SO4 to flow into the reaction flask. The reaction
should be immediate and vigorous and the pressure in the line should rise.

Add the D2SO4 drop by drop. Do not allow all of the D2SO4 to exit the dropping funnel
because it will introduce air into the vacuum system and convert your DCl to HCl. Stop the
reaction after no more than 3 minutes. A good spectrum can be obtained with relatively low
pressures, but you should shoot for at least 100 torr of gas collection.

When you have created enough gaseous product, close the valve on the IR cell. Do not add
any more D2SO4. Make sure the dropping funnel valve is closed.

Close the valve to the reaction flask, then open the vacuum pump cut off valve so that all the
gas in the line is cleared out and condensed in the liquid nitrogen trap.

While the line is clearing you need to remove any excess D2SO4 in the dropping funnel by
drawing it out the top using a disposable pipette. Pipette it into a beaker and then transport to
the sink. Flush with copious amounts of water.

Fill the dropping funnel with about 10 ml. This water will be dropped into the reaction flask
to quench the reaction.

Add the water to the reaction flask. Just like before, make sure you do not add all of it, which
would break the vacuum seal.

SLOWLY open the valve to the reaction flask and let the reaction flask clear out any
volatiles.

Close the manifold valve leading to the reaction vessel, remove it and clean thoroughly with
plenty of water and rinse with acetone. Be sure to wipe all vacuum grease off of the
glassware and joints.

Close the manifold valve leading to the IR cell and remove the IR cell. It is now ready for
analysis.

Keep the vacuum pump running. Youll need it to evacuate your IR cell.

2-8
Recording Spectra
You will be taking the IR spectrum using the Nicolet FTIR-200 spectrometer. The
fundamental details on how a Fourier transform IR instrument works can be found in
Appendix 1.

Nicolet FTIR-200 Spectrometer Operation

Be sure that the computer is booted up and that the spectrometer is turned on. Double
click on the EZ OMNIC icon on the desktop. Look in the upper right to be sure that there is a
check mark in the bench status to indicate that the program is communicating with the
spectrometer. (If a check is not there, notify your TA.) If the check is there, click on Collect
to open the menu and then click on experiment setup. On this window make sure that you have
the Collect tab selected. You now need to set the following:
Resolution:
No. of Scans:
Final format:
Correction:
Background Handling:

1 cm-1
64
Absorbance
None
Choose collect background before every sample

Now click on the bench tab and a window showing the IR parameters will appear.
Change to Max range to 4500 and the Min range to 1500. Click the OK button. This will return
you to the spectrum window.
Remove the lid from the spectrometer and click on the Col Sample icon. Type your
filename as the spectrum title and click the OK button. A confirmation window will pop up.
Click the OK button and wait until the background data collection is completed.
When the background collection is finished, a window will pop up to confirm that you
are ready to collect the spectrum on your sample. Insert the sample cell containing your HCl/DCl
sample into the spectrometer and then click the OK button on the conformation pop up window.
You can observe the data collection progress by looking at the boxes and the bottom left of the
screen. When the data collection for the sample is complete, click on Yes to Add to Window 1.
You should see a nicely resolved spectrum just below 3000 cm-1 for the HCl species and again a
little bit higher than 2000 cm-1 for the DCl species. The overtone spectrum for DCl shows up
around 4000 cm-1. Use the mouse to make a box around the spectrum and then click the left
mouse button to zoom in. Click on the Analyze menu and select find peaks. Peaks above the
movable black line will be assigned and you can also assign more peaks by clicking the mouse to
lower the black line. When you have finished with the assignment, click the replace button.
Note: You may rescale if needed by using the green arrows at the bottom of the screen. Print
this window. Repeat this procedure for the other IR band. When you have completed the
procedure for all the bands, close the program.

2-9
Clean-up

Reconnect the IR cell to the vacuum line and evacuate the cell.
Wait for two minutes then close the valves on the IR cell and the manifold.
Remove the IR cell from the line and place it in the desiccator.
Remove the dewar of liquid nitrogen from around the trap. Pour about half of the remain
liquid nitrogen out of the dewar.
Open the vacuum release valve (just above the rubber tube leading to the vacuum pump) and
turn off the vacuum pump.
You now need to remove the trap before it warms too much, put in the dewar and transport it
to the hood in the prep room. Remember that the trap contains condensed HCl and DCl, so it
needs to stay in the liquid nitrogen. Put the dewar and trap in the back corner where it will
not be disturbed and pull the hood sash down. Over time, the liquid nitrogen will boil off and
the HCL/DCL will vent out through the hood.
Make sure you put everything away clean and organized. It is your responsibility to make
sure everything is clean and ready to go for the next group, REGARDLESS OF HOW IT
WAS LEFT FOR YOU. Significant lab performance points will be lost if you fail to keep
the lab clean, organized and safe.

Data Analysis
Assigning the Spectrum
The first step in obtaining spectroscopic constants is to assign your spectrum. Several
methods may be used but the most obvious way for a diatomic molecule is to count outward
from the gap between the R and P branches. Remember that the P(0) line is the J = 0 J = 0
forbidden transition, so you will not see a peak for it. Next you need to tabulate the transition
frequencies of each isotope for later manipulation (H35Cl, H37Cl, D35Cl, and D37Cl). Dont
forget the DCl overtone spectrum as well. The accuracy of your results depends on how carefully
you record the spectra and read off the center of the line positions, so this step should be
performed with great care.
Finding Rotational Constants, B, using the irspec program.
A description of the underlying reasoning that is used to obtain the rotational constants
for a particular vibrational level is outlined here. First, consider the = 1 level. Note that if you
subtract the frequency of the P(J) line from the that of the R(J) line, the difference is given by

R(J) - P(J) = B1[(J + 2) (J + 1) J (J 1)]-De1 [(J + 2)2 (J + 1)2 J2 (J 1)2]

(14)

Where (J) is written as (J) for simplicity. This equation may be written as
R(J) P(J) = 2B1 (2J + 1) 4 De1 (2J + 1) (J2 + J + 1)
and then can be rearranged into a slope-intercept form of the equation
R( J ) P( J )
2 B1 4 De1 ( J 2 J 1)
2 J 1

(15)

(16)

2-10
So that a plot of [R(J) P(J)]/(2J + 1) versus (J2 + J + 1) can be use to obtain B1 and De1. To
obtain the rotational constants for the = 0 level, perform the same type of manipulation for
R(J-1) P(J + 1), whose difference is:
R(J 1) - P(J + 1) = B0(J + 1) (J + 2) - B0J(J 1)-De0[(J + 1)2 (J + 2)2 - J2(J 1)]

(17)

which simplifies to
R(J 1) - P(J + 1) = 2B0(2J + 1) - 4De0 (2J + 1) (J2 + J + 1)

(18)

These equations apply to both the HCl and DCl species.

Obtaining the Rotational Constants using Excel
1. Assign the P and R transitions for a particular vibrational transition. Enter your assignments
of J and the transition energies into an Excel data sheet. We recommend a new data sheet for
each vibrational transition.
2. Now you will find the rotational constant B1 and De1 by curve fitting a plot of equation 16.
3. To obtain the values of B0 and De0 again) you will perform a similar rearrangement as in step
2, but you should perform it with the slope intercept form of equation 18. Once again you
recast these equations in linear form, transform your raw data appropriately, perform a linear
plot and analysis, and obtain the parameters from the slope and intercept.
Finding Molecular Parameters
Using the B values and equation (2), you can obtain Be for each isotope. Subsequently, you can
calculate the equilibrium bond length and the average bond length for each isotope and
vibrational level. If the assumptions we have made are all correct, re and should be
independent of isotope. Is this true within the precision of the data?
Sample Calculations
Given that
B0 = Be - (0 + 1/2) and B1 = Be - (1 + 1/2), the difference is B0 B1 = .
Once you evaluate , substitute it back into the equation and determine Be. Use equations 3 to
solve for the equilibrium internuclear distance (re).
The Laboratory Report
Include the data that you obtained experimentally and the spectra with the line positions labeled.
Include a table of B0, B1, De0, De1, Be , and re for each isotope; H35Cl, H37Cl, D35Cl and D37Cl.
Be sure to also include a sample calculation for each type of calculation performed. Compare
your values with those given in references 3-5. You should include percent error calculations
assuming the literature value to be correct.
Items to include in your discussion
1. Do the values of the spectroscopic constants Be, B and De, vary with isotope and/or with
vibrational level in a way that you would expect?
2. Does re change for each isotope? Explain your answers.
3. In general, what accounts for the uneven spacing on the lines in the P and R branches of a
vibration-rotation spectrum?

2-11
4. The constant B2 for DCl can be obtained by following a procedure analogous to that used to
find B1 but using the overtone spectrum (= 0 2). Determine B2 and De2 for each DCl
isotope.
5. Use the Boltzmann distribution equation (5) to model what the intensities of the absorption
peaks should be for your experimental data. Does you data match this theory? How would
the distribution change at higher temperatures?
6. Manipulate (using equation 1) the R(0) and P(1) line frequencies for both the fundamental
and overtone spectra of DCl to obtain e and eXe, where e is the frequency at which the Q
branch would appear if it were an allowed transition. You will need to use equation (1) for
four different line frequencies:
EA = E( = 0, J = 0 = 1, J = 1)
EB = E( = 0, J = 0 = 2, J = 1)
EC = E( = 0, J = 1 = 1, J = 0)
ED = E( = 0, J = 1 = 2, J = 0).
7. What additional spectroscopic information could be obtained from your data? Be as detailed
as possible.
References

1. Atkins, P. W. and R. S. Friedman. Molecular Quantum Mechanics. 3rd Ed. New York:
Oxford, 1997. Reserve QD 462.A84 1997.
2. Harris, D. C. and M. D. Bertolucci. Symmetry and Spectroscopy. New York: Dover, 1978.
Reserve QD 96.V53 H37.
3. De Lucia, F.C, Helminger, P., Gordy, W. Submillimeter-Wave Spectra and Equilibrium
Structures of the Hydrogen Halides, Phys. Rev. A, 1971, 3, 18491857.
4. Rank, D.H., Eastman, D.P., Rao, S., and Wiggins, T.A., Rotational and Vibrational Constants
of the HC35 and DCl35 Molecules, J. of the Optical Society of America, 1962, 52(1), 1-7.
5. http://physics.nist.gov/PhysRefData/MolSpec/Diatomic/Html/Tables/HCl.html
6. http://hyperphysics.phy-astr.gsu.edu/hbase/molecule/vibrot.html
7. Pauling, L. and E. B. Wilson. Introduction to Quantum Mechanics. New York: Dover 1935.
Reserve QC 174.12.P39 1985.
8. Shoemaker, D.P., Garland, C.W., Nibler, J.W. Experiments in Physical Chemistry, 6th Ed.
McGraw Hill, NY, 1996.
9. Sime, R. J. Physical Chemistry: Methods, Techniques and Experiments. New York:
Saunders, 1990. Reserve QD 453.2.S524 1990.
10. Steinfeld, J. Molecules and Radiation. Boston: MIT Press, 1985. Reserve QC 454.M6 S83
1985.
11. Willard, H. H., et al. Instrumental Methods of Analysis. 7th Ed. New York: Van Nordstrand,
1988. Reserve QD 79.I5 I52 1988.
*This lab is adapted from Shoemaker et. al., 1996.

2-12
Appendix A: The Fourier Transform Intrared (FTIR) Method
This discussion follows that given by J. Moore, et al. in Building Scientific Apparatus.
Collimated illumination (obtained from a laser, or parallel light obtained by placing a point
source at the focal point of a converging lens) is divided into two equal parts at a beamsplitter
and sent to two plane mirrors M1 and M2 (Fig. 1). If observations of a broad-band (temporally
incoherent0 source are being made, a compensating plate of the same material and thickness as
the beamsplitter is included in Arm 2 of the interferometer. This plate compensates for the two
additional transits of the beamsplitter substrate made by the beam in Arm 1.

Figure 2: Schematic of an interferometer.

Maxima in the detected output occur when 2l = m, where 2l is the path difference in the
two arms, m is an integer, and is the wavelength of light. Assuming monochromatic radiation
of angular frequency (= 2 /c), the fields of the lighwaves in Arms 1 and 2 can be represented
as
E1 E0ei ( t 1 , E2 E0e( t 2
(6)
The output intensity is proportional to the square modules of the electric field
I

E1 E2

(7)

2-13
Hence, we find
E1 E 2

E 0 ei t 1 E 0 ei t 2 E 0 e i 1 E 0 e i t 2
E 02 1 e i 1 2 ei 1 2 1

(8)

2 E 02 2 E 02 cos 2 1
or
E1 E2

I 0 1 cos

(9)

where = 2m and I0 = E 02 . Since m = 2l/ = 2l(/c),

4 v l
I I 0 1 cos

(10)

Because we are performing spectroscopy, we wish to consider the full frequency

dependence of the signal. If the light source has an intensity I() at the frequency , then the
detected intensity in the interval d is given by

4 v l
I (v) 1 cos
dv
c

I v l

(11)

where l is the pathlength change. If the mirror is moving at a constant velocity , then l = t
where t is the time. The integrated intensity is
I (l )

4 v l
I v 1 cos
dv
c

v 0

I0
4 v l
I v 1 cos
dv
0

2
c

(12)

The second term is the cosine transform of I(). Hence, the frequency domain spectrum of the
detected light can be determined by taking the inverse transform, namely
I v

2
c

l 0

4 l v
I

dl
I (l ) 0 cos
2
c

(13)

2-14
Figure 3: Schematic of a Fourier transform instrument.
For example if a HeNe laser is used as a references
source in a FT instrument (figure 3), a signal I(x) as
a function of the displacement of the mirror (x), an
interference pattern is observed at the detector
(Figure 4). If the mirror is moved at a constant rate
= dx/dt, the detector signal oscillates at the
frequency y = 2 , since the path difference
changes at twice the rate of mirror movement.
Thus, for = 1000 cm-1 and = 1 mm/s, the
resulting oscillation occurs at 200 Hz. A typical
real interferogram and spectrum are shown in
Figure 5.
Figure 4: A plot of the predicted
interference pattern.

Figure 5: A plot of an interferogram and its corresponding spectrum.