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What is Spectroscopy?
Spectroscopy pertains to the dispersion of an object's light into its component colors (i.e.
energies). By performing this dissection and analysis of an object's light, astronomers can
infer the physical properties of that object (such as temperature, mass, luminosity and
composition).

But before we hurtle headlong into the wild and woolly field of spectroscopy, we need to
try to answer some seemingly simple questions, such as what is light? And how does it
behave? These questions may seem simple to you, but they have presented some of the
most difficult conceptual challenges in the long history of physics. It has only been in this
century, with the creation of quantum mechanics that we have gained a quantitative
understanding of how light and atoms work.

The Nature of Light

To understand the processes in astronomy that generate light, we must realize first that
light acts like a wave. Light has particle-like properties too, so it's actually quite a twisted
beast (which is why it took so many years to figure out). But right now, let's just explore
light as a wave.

Picture yourself wading around on an ocean beach for a moment, and watch the many
water waves sweeping past you. Waves are disturbances, ripples on the water, and they
possess a certain height (amplitude), with a certain number of waves rushing past you
every minute (the frequency) and all moving at a characteristic speed across the water
(the wave speed). Notice the distance between successive waves? That's called the
wavelength.
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Keeping this analogy in mind, let's leave the ocean beach for a while and think about
light like a wave. The wave speed of a light wave is simply the speed of light, and
different wavelengths of light manifest themselves as different colors! The energy of a
light wave is inversely-proportional to its wavelength; in other words, low-energy waves
have long wavelengths, and high-energy light waves have short wavelengths.

The Electromagnetic Spectrum

Physicists classify light waves by their energies (wavelengths). Labeled in increasing
energy, we might draw the entire electromagnetic spectrum as shown in the figure below:

The Electromagnetic Spectrum. Notice how small the visible region of the spectrum is, compared to the
entire range of wavelengths.

Notice that radio, TV, and microwave signals are all light waves, they simply lie at
wavelengths (energies) that your eye doesn't respond to. On the other end of the scale,
beware the high energy UV, x-ray, and gamma-ray photons! Each one carries a lot of
energy compared to their visible- and radio-wave brethren. They're the reasons you
should wear sunblock, for example.

The above spectrum of light can also be represented as follows:

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In wavenumbers, the mid IR ranges is 4000-400 cm-1. An increase in wavenumber

corresponds to an increase in energy. As we shall see later, this is a convenient
relationship for the organic chemist.

Infrared radiation is absorbed by organic molecules and converted into energy of

molecular vibration. In IR spectroscopy, an organic molecule is exposed to infrared
radiation. When the radiant energy matches the enrgy of a specific molecular vibration,
absorption occurs. A typical IR spectrum is shown below. The wavenumber, plotted on
the X-axis, is proportional to energy; therefore, the highest energy vibrations are on the
left. The percent transmittance (%T) is plotted on the Y-axis. An absorption of radiatiant
energy is therefore represented by a “trough” in the curve: zero transmittance corresponds
to 100% absorption of light at that wavelength.
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Infrared Spectroscopy

Infrared, or IR, spectroscopy is one type of vibrational spectroscopy, which, as you might
have guessed, is a spectroscopic technique where molecular vibrations are analyzed. To
fully understand IR spectroscopy, you must first understand the principles of simple
harmonic motion.

Imagine two spheres, or masses, connected with a spring. In case you are confused, what
you are imagining should look roughly like this.

This is what is known as a simple harmonic oscillator. Once set into motion, the sphere
will oscillate, or vibrate back and forth on the spring, at a certain frequency depending on
the masses of the spheres and the stiffness of the spring. A sphere with a small mass is
lighter and easier to move around than one with a large mass. Therefore, smaller masses
oscillate at a higher frequency than larger masses. A very stiff spring, like a bedspring, is
hard to deform and quickly returns to it's original shape when the deforming force is
removed. On the other hand, a weak spring is easily deformed and takes much longer to
return to it's shape. Therefore, a stiffer spring will oscillate at a higher frequency than a
weak one. A chemical bond between two atoms can be thought of as a simple harmonic
oscillator. The bond is the spring, and the two atoms, or groups of atoms, connected by
the bond are the masses. Every atom has a different mass, and single, double and triple all
have different stiffnesses, and therefore each combination of atoms and bonds has its own
characteristic harmonic frequency.

Many physical systems, such as a weight suspended with a spring, experience a linear
restoring force when displaced from their equilibrium position. The mathematical
expression for such a restoring force, F, is:

F = −kx

k is a proportionality constant called the force constant and x is the displacement from
the equilibrium position. This relationship is called Hooke's law. For the spring example,
k will be large for a stiff spring and smaller for springs that are weaker. Similarly, if you
stretch a spring twice as far, it "springs back" with twice the force. Of course this law is
valid for limited values of x. Try stretching a spring too far and you'll find that the
restoring force is no longer directly proportional to displacement!

The potential energy, V, for a one-dimensional system is equal to the negative of the
force integrated over x:

V(x) =   Fdx = k∫ xdx = ½ kx² + constant

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The constant of integration depends on the physical system being modeled. For the
ground state of a diatomic molecule, as modeled below, we can set it to zero.

Harmonic Oscillator Model for a Diatomic Molecule

We can model the bond in a molecule as a spring connecting two atoms and use the
harmonic oscillator expression to describe the potential energy for the periodic vibration
of the atoms. The potential energy, V(x), of a particle moving in one dimension is given
by:

V(x) = ½ kx²

where k is the force constant as above and the constant of integration is zero. We can
make this expression more useful by changing x to R-Re, where R is the internuclear
distance (the distance between atoms) and Re is the equilibrium internuclear distance (the
bond length):

V(R) = ½ k(R − Re)²

The following figure shows the ground-state potential energy curve (called a potential
well) for the H2 molecule using the harmonic oscillator model. Re for H2 is 0.7412 Å.
There is one obvious deficiency in the model, it does not show the energy at which the
two atoms dissociate, which occurs at 4.748 eV for the H2 molecule (1 eV = 8065.48 cm-
1
). At some internuclear distance the atoms are far enough apart so that they do not "feel"
each other. That is, they are isolated and the bond is broken.
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The solid blue horizontal lines show the energy levels that are calculated using the
harmonic oscillator model:

Ev = (v + ½) νe

where v is the vibrational quantum number (v = 0,1,2,...). The v = 0 level is the

vibrational ground state and is the lowest horizontal line in the plot.

νe is called the vibrational constant:

νe = ½ πc (k/)

where µ is the reduced mass (m1m2/m1+m2). The simple harmonic oscillator provides a
good fit to energies for the lowest energy levels, but fails at higher energies.

A more realistic model of the potential well of a diatomic molecule is the Morse
potential, which does model the dissociation energy.
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Morse Potential
The potential energy, V(R), of a diatomic molecule can be described by the Morse
potential:

V(R) = De(1 − 2(R-R ))

e

where De is the well depth, R is internuclear distance, Re is the equlibrium internuclear

distance (bond length), and

β =  e (2/De)

νe is the vibrational constant and µ is the reduced mass.

The following figure shows the ground state potential well of the H2 molecule. The curve
is calculated from the Morse potential and the energy levels are calculated using the
harmonic oscillator model with the first anharmonic correction.
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Do is the dissociation energy, which is slightly different from the well depth, De. The
vibrational energy levels in this plot are calculated from:

Ev = (v + ½) νe - (v + ½)² νexe + (v + ½)³ νeye + higher terms

where v is the vibrational quantum number, v = 0,1,2,..., and xe and ye are the first and
second anharmonicity constants, respectively. The v = 0 level is the vibrational ground
state.

The complexity of this spectrum is typical of most infrared spectra, and illustrates their
use in identifying substances. The gap in the spectrum between 700 & 800 cm-1 is due to
solvent (CCl4) absorption. Further analysis (below) will show that this spectrum also
indicates the presence of an aldehyde function, a phenolic hydroxyl and a substituted
benzene ring. The inverted display of absorption, compared with UV-Visible spectra, is
characteristic. Thus a sample that did not absorb at all would record a horizontal line at
100% transmittance (top of the chart).

The frequency scale at the bottom of the chart is given in units of reciprocal
centimeters (cm-1) rather than Hz, because the numbers are more manageable. The
reciprocal centimeter is the number of wave cycles in one centimeter; whereas, frequency
in cycles per second or Hz is equal to the number of wave cycles in 3*1010 cm (the
distance covered by light in one second). Wavelength units are in micrometers, microns
(μ), instead of nanometers for the same reason. Most infrared spectra are displayed on a
linear frequency scale, as shown here, but in some older texts a linear wavelength scale is
used. A calculator for interconverting these frequency and wavelength values is provided
on the right. Simply enter the value to be converted in the appropriate box, press
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"Calculate" and the equivalent number will appear in the empty box.
Infrared spectra may be obtained from samples in all phases (liquid, solid and gaseous).
Liquids are usually examined as a thin film sandwiched between two polished salt plates
(note that glass absorbs infrared radiation, whereas NaCl is transparent). If solvents are
used to dissolve solids, care must be taken to avoid obscuring important spectral regions
by solvent absorption. Perchlorinated solvents such as carbon tetrachloride, chloroform
and tetrachloroethene are commonly used. Alternatively, solids may either be
incorporated in a thin KBr disk, prepared under high pressure, or mixed with a little non-
volatile liquid and ground to a paste (or mull) that is smeared between salt plates.

2. Vibrational Spectroscopy

A molecule composed of n-atoms has 3n degrees of freedom, six of which are

translations and rotations of the molecule itself. This leaves 3n-6 degrees of vibrational
freedom (3n-5 if the molecule is linear). Vibrational modes are often given descriptive
names, such as stretching, bending, scissoring, rocking and twisting. The four-atom
molecule of formaldehyde, the gas phase spectrum of which is shown below, provides an
example of these terms. If a ball & stick model of formaldehyde is not displayed to the
right of the spectrum, press the view ball&stick model button at the lower right. We
expect six fundamental vibrations (12 minus 6), and these have been assigned to the
spectrum absorptions. To see the formaldehyde molecule display a vibration, click one of
the buttons under the spectrum.

Gas Phase Infrared Spectrum of Formaldehyde, H2C=O

The exact frequency at which a given vibration occurs is determined by the strengths of
the bonds involved and the mass of the component atoms. In practice, infrared spectra do
not normally display separate absorption signals for each of the 3n-6 fundamental
vibrational modes of a molecule. The number of observed absorptions may be increased
by additive and subtractive interactions leading to combination tones and overtones of the
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fundamental vibrations, in much the same way that sound vibrations from a musical
instrument interact. Furthermore, the number of observed absorptions may be decreased
by molecular symmetry, spectrometer limitations, and spectroscopic selection rules. One
selection rule that influences the intensity of infrared absorptions, is that a change in
dipole moment should occur for a vibration to absorb infrared energy. Absorption bands
associated with C=O bond stretching are usually very strong because a large change in
the dipole takes place in that mode.
Some General Trends:

i) Stretching frequencies are higher than corresponding bending frequencies. (It

is easier to bend a bond than to stretch or compress it.)
ii) Bonds to hydrogen have higher stretching frequencies than those to heavier
atoms.
iii) Triple bonds have higher stretching frequencies than corresponding double
bonds, which in turn have higher frequencies than single bonds. (Except for bonds
to hydrogen).

The general regions of the infrared spectrum in which various kinds of vibrational bands
are observed are outlined in the following chart. Note that the blue colored sections above
the dashed line refer to stretching vibrations, and the green colored band below the line
encompasses bending vibrations. The complexity of infrared spectra in the 1450 to 600
cm-1 region makes it difficult to assign all the absorption bands, and because of the
unique patterns found there, it is often called the fingerprint region. Absorption bands in
the 4000 to 1450 cm-1 region are usually due to stretching vibrations of diatomic units,
and this is sometimes called the group frequency region.

Infrared Absorbances for

Common Functional Groups

Group Frequencies

Detailed information about the infrared absorptions observed for various bonded atoms
and groups is usually presented in tabular form. The following table provides a collection
of such data for the most common functional groups. Since most organic compounds
have C-H bonds, a useful rule is that absorption in the 2850 to 3000 cm-1 is due to sp3 C-
H stretching; whereas, absorption above 3000 cm-1 is from sp2 C-H stretching or sp C-H
stretching if it is near 3300 cm-1.
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 Alcohols and amines display strong broad O-H and N-H stretching bands in the
region 3400-3100 cm . The bands are broadened due to hydrogen bonding and a
sharp 'non-bonded' peak can often be seen at around 3400 cm .
 Alkene and alkyne C-H bonds display sharp stretching absorptions in the region
3100-3000 cm . The bands are of medium intensity and are often obscured by
other absorbances in the region (i.e., OH).
 Triple bond stretching absorptions occur in the region 2400-2200 cm .
Absorptions from nitriles are generally of medium intensity and are clearly
defined. Alkynes absorb weakly in this region unless they are highly asymmetric;
symmetrical alkynes do not show absorption bands.
 Carbonyl stretching bands occur in the region 1800-1700 cm . The bands are
generally very strong and broad. Carbonyl compounds which are more reactive in
nucleophilic addition reactions (acyl halides, esters) are generally at higher wave
number than simple ketones and aldehydes, and amides are the lowest, absorbing
in the region 1700-1650 cm .
 Carbon-carbon double bond stretching occurs in the region around 1650-1600 cm
. The bands are generally sharp and of medium intensity. Aromatic compounds
will typically display a series of sharp bands in this region.
 Carbon-oxygen single bonds display stretching bands in the region 1200-1100 cm
. The bands are generally strong and broad. You should note that many other
functional groups have bands in this region which appear similar.

IR Absorbances of Common Functional Groups

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The infrared spectrum of benzyl alcohol displays a broad, hydrogen-bonded OH

stretching band in the region 3400 cm , a sharp unsaturated (sp ) CH stretch at about
3010 cm and a saturated (sp ) CH stretch at about 2900 cm ; these bands are typical
for alcohols and for aromatic compounds containing some saturated carbon. Acetylene
(ethyne) displays a typical terminal alkyne C H stretch, as shown in the second panel.

Saturated and unsaturated CH bands also shown clearly in the spectrum of vinyl acetate
(ethenyl ethanoate). This compound also shows a typical ester carbonyl at 1700 cm
and a nice example of a carbon-carbon double bond stretch at about 1500 cm . Both of
these bands are shifted to slightly lower wave numbers than are typically observed (by
about 50 cm ) by conjugation involving the vinyl ester group
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The following table is a more detailed description of IR frequencies of typical functional

groups:

Typical Infrared Absorption Frequencies

Stretching Vibrations Bending Vibrations
Functional Inte Range Inte
Range (cm-1) Assignment Assignment
Class nsity (cm-1) nsity
Alkanes 2850-3000 str CH3, CH2 & CH 1350- med CH2 & CH3
2 or 3 bands 1470 med deformation
1370- wk CH3
1390 deformation
720- CH2 rocking
725
Alkenes 3020-3100 med =C-H & =CH2 880- str =C-H &
1630-1680 var (usually sharp) 995 med =CH2
C=C (symmetry 780- med (out-of-plane
1900-2000 str reduces intensity) 850 bending)
675- cis-
C=C asymmetric 730 RCH=CHR
stretch
Alkynes 3300 str C-H (usually 600- str C-H
2100-2250 var sharp) 700 deformation
C≡C (symmetry
reduces intensity)
Arenes 3030 var C-H (may be 690- str- C-H bending
1600 & 1500 med- several bands) 900 med &
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wk C=C (in ring) (2 ring

bands) puckering
(3 if conjugated)
Alcohols & 3580-3650 var O-H (free), 1330- med O-H bending
Phenols 3200-3550 str usually sharp 1430 var- (in-plane)
970-1250 str O-H (H-bonded), 650- wk O-H bend
usually broad 770 (out-of-
C-O plane)
Amines 3400-3500 (dil. wk N-H (1°-amines), 1550- med- NH2
soln.) wk 2 bands 1650 str scissoring
3300-3400 (dil. med N-H (2°-amines) 660- var (1°-amines)
soln.) C-N 900 NH2 & N-H
1000-1250 wagging
(shifts on H-
bonding)
Aldehydes & 2690-2840(2 med C-H (aldehyde C-
Ketones bands) str H) 1350- str α-CH3
1720-1740 str C=O (saturated 1360 str bending
1710-1720 aldehyde) 1400- med α-CH2
str C=O (saturated 1450 bending
1690 str ketone) 1100 C-C-C
1675 str bending
1745 str aryl ketone
1780 α, β-unsaturation
cyclopentanone
cyclobutanone
Carboxylic 2500-3300 (acids) str O-H (very broad) 1395- med C-O-H
Acids & overlap C-H str C=O (H-bonded) 1440 bending
Derivatives 1705-1720 (acids) med- O-C (sometimes
1210-1320 (acids) str 2-peaks)

1785- str C=O

1815 str C=O (2-bands)
( acyl str O-C
halides) str C=O med
1750 & str O-C (2-bands) 1590- med N-H (1¡-
1820 str C=O (amide I 1650 amide) II
(anhydrid band) 1500- band
es) 1560 N-H (2¡-
1040- amide) II
1100 band
1735-
1750
(esters)
1000-
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1300
1630-
1695(ami
des)
Nitriles 2240-2260 med C≡N (sharp)

Isocyanates,Iso 2100-2270 med -N=C=O,

thiocyanates, -N=C=S
Diimides, -N=C=N-, -N3,
Azides & C=C=O
Ketenes

To illustrate the usefulness of infrared absorption spectra, examples for five C4H8O
isomers are presented below their corresponding structural formulas.
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4. Other Functional Groups

Infrared absorption data for some functional groups not listed in the preceding table are
given below. Most of the absorptions cited are associated with stretching vibrations.
Standard abbreviations (str = strong, wk = weak, brd = broad & shp = sharp) are used to
describe the absorption bands.

Functional Class Characteristic Absorptions

Sulfur Functions
S-H thiols 2550-2600 cm-1 (wk & shp)
S-OR esters 700-900 (str)
S-S disulfide 500-540 (wk)
C=S thiocarbonyl 1050-1200 (str)
S=O sulfoxide 1030-1060 (str)
sulfone 1325± 25 (as) & 1140± 20 (s) (both str)
sulfonic acid 1345 (str)
sulfonyl chloride 1365± 5 (as) & 1180± 10 (s) (both str)
sulfate 1350-1450 (str)
Phosphorous Functions
P-H phosphine 2280-2440 cm-1 (med & shp)
950-1250 (wk) P-H bending
(O=)PO-H phosphonic acid 2550-2700 (med)
P-OR esters 900-1050 (str)
P=O phosphine oxide 1100-1200 (str)
phosphonate 1230-1260 (str)
phosphate 1100-1200 (str)
phosphoramide 1200-1275 (str)
Silicon Functions
Si-H silane 2100-2360 cm-1 (str)
Si-OR 1000-11000 (str & brd)
Si-CH3 1250± 10 (str & shp)
Oxidized Nitrogen Functions
=NOH oxime
O-H (stretch) 3550-3600 cm-1 (str)
C=N 1665± 15
N-O 945± 15
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N-O amine oxide

aliphatic 960± 20
aromatic 1250± 50
N=O nitroso 1550± 50 (str)
nitro 1530± 20 (as) & 1350± 30 (s)

Test your ability to use information from infrared and mass spectrometry to identify an
unknown compound. Clicking the button opens a display in which four different
problems of this kind may be selected. Answers are provided once an effort to solve the
problem has been made.

http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/InfraRed/infrared.htm

http://pslc.ws/mactest/irabs.htm