Infrared Spectrometry: (Wen-Hui Cheng)

Infrared Spectrometry
鄭文惠 (Wen-Hui Cheng)
Department of Materials Science and Engineering,

National Cheng Kung University
wcheng@gs.ncku.edu.tw
Academic Year 112 Semester 1

NCKU / MSE
Infrared Spectrometry
• The infrared (IR) region of the spectrum encompasses radiation with

wavenumbers ranging from about 12,800 to 10 cm-1 or wavelengths from
0.78 to 1000 μm.
• The foundations of modern Fourier Transform Infrared Spectroscopy

(FTIR) were laid in the latter part of the nineteenth century by Michelson
and Lord Rayleigh who recognized the relationship of an interferogram to
its spectrum by a Fourier transformation.
• It was not until the advent of computers and the fast Fourier algorithm that
interferometry began to be applied to spectroscopic measurements in the
1970s.
Advanced Characterization of Materials 4747

IR Absorption Spectrum
• Note that the horizontal scale

changes at 2000 cm-1, permitting
easier identification of the numerous
IR bands that appear in the lower
wavenumber region.
IR Absorption
• IR radiation is not energetic enough to bring about the kinds of electronic

transitions with UV and visible radiation. Absorption of IR radiation is thus
confined largely to molecular species that have small energy differences
between various vibrational and rotational states.
• To absorb IR radiation, a molecule must undergo a net change in dipole

moment as it vibrates or rotates.
• The dipole moment is determined by the magnitude of the charge difference

and the distance between the two centers of charge.
• If the frequency of the radiation exactly matches a natural vibrational

frequency of the molecule, absorption of the radiation takes place that
produces a change in the amplitude of the molecular vibration.
• The rotation of asymmetric molecules around their centers of mass also

results in periodic dipole moment fluctuations that allow interaction with the
radiation field.

Rotation and Vibration
• No net change in dipole moment occurs during the vibration or rotation of

homonuclear species such as O2, N2, or Cl2. As a result, such compounds
cannot absorb IR radiation.
Rotational Transitions
• The energy required to cause a change in rotational level is quite small and
corresponds to radiation of 100 cm-1. Because rotational levels are
quantized, absorption by gases in this far-IR region is characterized by
discrete, well-defined lines. In liquids or solids, intramolecular collisions and
interactions cause broadening of the lines into a continuum.
Vibrational-Rotational Transitions
• Vibrational energy levels are also quantized, and for most molecules the
energy differences between quantum states correspond to the mid-IR region.
The IR spectrum of a gas usually consists of a series of closely spaced lines,
because there are several rotational energy levels for each vibrational level.
On the other hand, rotation is highly restricted in liquids and solids, leaving
only somewhat broadened vibrational bands.

Vibration
• Vibrations fall into the basic

categories of stretching and
bending.
• A stretching vibration involves a

continuous change in the
interatomic distance along the axis
of the bond between two atoms.
• Bending vibrations are

characterized by a change in the
angle between two bonds and are
of four types: scissoring, rocking,
wagging, and twisting.

Stretching Vibration
The displacement of the molecule can be expressed by using Hook’s law as
𝑚! 𝑚" 𝑑 " 𝑥! 𝑑 " 𝑥"

+ = −𝐾(𝑥! + 𝑥" )
𝑚! + 𝑚" 𝑑𝑡 " 𝑑𝑡 "
𝑚! 𝑚"
By replacing the reduced mass 𝜇 = and total displacement 𝑞 = 𝑥! + 𝑥"
𝑚! + 𝑚"
𝑑" 𝜇
𝜇 " = −𝐾𝑞
𝑑𝑡
!
By solving the above equation, we get 𝑞 = 𝑞! cos(2π𝜈" 𝑡) where 𝜈# =
"$
𝐾/𝜇
vibrational frequency

Stretching Vibration
in wavenumbers
• k has been found to lie around 5 x102 N/m for most single bonds, with
double and triple bonds having force constants of about two and three
times.
Example: Calculate the approximate wavenumber of the fundamental absorption
due to the stretching vibration of a carbonyl group C=O.
The carbonyl stretching band is found experimentally to be in

the region of 1600 to 1800 cm-1 (6.3 to 5.6 μm).
Quantum Treatment of Vibrations
where h is Planck’s constant, and v is

the vibrational quantum number, which
can take only positive integer values
(including zero)
selection rule states that ∆v = ±1.
• At higher quantum numbers, ΔE becomes smaller, and the selection rule is not
rigorously followed. As a result, weaker transitions called overtones are
sometimes observed. These transitions correspond to ∆v = ±2 or ±3.

Vibrational Modes
• A molecule containing N atoms have 3N degrees of freedom.
• In defining the motion of a molecule, we need to consider

(1) The motion of the entire molecule through space (that is, the translational
motion of its center of gravity) (3 degrees of freedom)
(2) The rotational motion of the entire molecule around its center of gravity (3
degrees of freedom)
(1) The motion of each of its atoms relative to the other atoms, or in other
words, its individual vibrations. (3N-6 degrees of freedom -> normal mode)
• A linear molecule is a lacking in rotation about the bond axis, and only two
degrees of freedom suffice to describe rotational motion. Thus, the number of
vibrations for a linear molecule is given by 3N-5.

Absorption Bands
Fewer Absorption Bands
(1) The symmetry of the molecules is such that no change in dipole moment
results from a particular vibration
(2) The energies of two or more vibrations are identical or nearly identical
(3) The absorption intensity is so low as to be undetectable by ordinary means
(4) The vibrational energy is in a wavelength region beyond the range of the
instrument used to measure absorption
More Absorption Bands

(1) Weaker transitions called overtone bands that occur at two or three times
the frequency of the fundamental frequency.
(2) Combination bands are sometimes encountered when a photon excites
two vibrational modes simultaneously.

Vibrational Coupling
1. Strong coupling between stretching vibrations occurs only when there is

an atom common to the two vibrations.
2. Interaction between bending vibrations requires a common bond between

the vibrating groups.
3. Coupling between a stretching and a bending vibration can occur if the

stretching bond forms one side of the angle that varies in the bending
vibration.
4. Interaction is greatest when the coupled groups have individual energies

that are nearly equal.
5. Little or no interaction is observed between groups separated by two or

more bonds.
6. Coupling requires that the vibrations be of the same symmetry species.

IR Spectrum of Carbon Dioxide
• C=O stretching vibration, about 1700 cm-1, or 6 μm.
• Experimentally, carbon dioxide exhibits two absorption maxima, one at 2350

cm-1 (4.3 μm) and the other at 667 cm-1 (15 μm).
• Carbon dioxide is a linear molecule and thus has (3X3) - 5 = 4 normal modes.
• Two stretching vibrations are possible; furthermore, interaction between the

two can occur because the bonds involved are associated with a common
carbon atom. As can be seen, one of the coupled vibrations is symmetric and
the other is asymmetric.
no change in dipole moment a net change in charge distribution

-> IR inactive occurs periodically
-> absorption at 2350 cm-1

IR Spectrum of Carbon Dioxide
• The remaining two vibrational modes of carbon dioxide involve scissoring.
• The two vibrations are identical in energy and thus produce a single absorption
band at 667 cm-1. Quantum states that are identical, as these are, are said to be
degenerate.
• For nonlinear, triatomic molecule such as water, sulfur dioxide, or nitrogen
dioxide -> (3X3) - 6 = 3
Illustrates how IR absorption spectroscopy can sometimes be used

to deduce molecular shapes.
Vibrational Coupling
• Coupling of vibrations is a common phenomenon. As a result, the position of

an absorption band corresponding to a given organic functional group cannot
be specified exactly.
• For example, the C-O stretching frequency in methanol is 1034 cm-1 (9.67
μm), in ethanol it is 1053 cm-1 (9.50 μm), and in 2-butanol it is 1105 cm-1 (9.05
μm). These variations result from a coupling of the C-O stretching with
adjacent C-C stretching or C-H vibrations.
• Although interaction effects may lead to uncertainties in the identification of

functional groups contained in a compound, it is this very effect that provides
the unique features of an IR absorption spectrum that are so important for the
positive identification of a specific compound.

IR Instrumentation
• Three types of instruments for

IR absorption measurements
are commonly available:
(1) Dispersive spectrophotometers

with a grating monochromator.
(2) FT spectrometers employing

an interferometer.
(speed, reliability, signal-to-noise
advantage, and convenience)
(3) Nondispersive photometers

using a filter or an absorbing gas
that are used for analysis of
atmospheric gases at specific
wavelengths.

IR Source
• IR sources consist of an inert solid that is heated electrically to a

temperature between 1500 and 2200 K. These sources produce continuum
radiation approximating that of a blackbody.
• The maximum radiant intensity at

these temperatures occurs between
5000 and 5900 cm-1 (2 and 1.7 μm).
• At longer wavelengths, the intensity

falls off smoothly.
• On the short wavelength side, the

decrease is much more rapid, and a
reduction in intensity to 1% is
observed at about 10,000 cm-1 (1 μm).

Michelson Interferometer
• Although the light from the source is

incoherent, when it is split into two
components by the beam splitter, the
components are coherent and can
produce interference phenomena when
the beams are combined.
• The detector output—the

interferogram—consists of a series of
maxima and minima that can be
described by the equation
When the source emits more than one frequency
B(f) is the source intensity modified by the sample

The interferogram becomes narrower as f1 is increased.

• The interferogram always retains its maximum at x = 0 where L1 = L2,

because all wavelengths interfere constructively for that mirror position.
à centerburst
• There is a practical limit to the mirror
displacement, represented by x = L. The
best spectral resolution is ∆f = 1/L.
• In practice, other practical considerations

reduce ∆f below this value.
• In most FTIR instruments, numerous

movable mirror sweeps are averaged for
enhanced signal-to-noise ratio.
• B(f) contains the spectral content of the source, the sample, and the ambient
in the path of the measurement. It is common practice to reduce atmospheric
H2O and CO2 absorption lines by purging the apparatus with dry nitrogen.

Example

FTIR Spectrometers
• FTIR spectrometers can be single-beam or double-beam instruments.
• The lower curve reveals that atmospheric water and carbon dioxide absorb
radiation in some important spectral regions and can cause serious interference
problems.
• The upper curve shows that the reference beam compensates nearly perfectly
for absorption by both compounds. A stable 100%T baseline results.

Single VS. Double Beam
single-beam
double-beam

IR Transducers
IR transducers are of three general types:
(1) Pyroelectric transducers (ex: Triglycine sulfate)

When an electric field is applied across any dielectric material, polarization takes
place, with the magnitude of the polarization being a function of the dielectric
constant of the material. Pyroelectric substances, retain a strong temperature-
dependent polarization after removal of the field. Changing its temperature by
irradiating it with IR radiation alters the charge distribution across the crystal,
which can be detected as a current in an external electrical circuit.
(2) Photoconducting transducers (faster and more sensitive)(ex: lead sulfide,

indium antimonide)
Absorption of radiation by these materials promotes nonconducting valence
electrons to a higher energy-conducting state, thus decreasing the electrical
resistance of the semiconductor. They must be cooled with liquid nitrogen (77 K)
to minimize thermal noise.
(3) Thermal transducers (too slow to be used in FTIR)

Sample Handling
• Water and the alcohols are difficult to use as solvents in IR spectrometry.
• Water and alcohols also attack alkali-metal halides, the most common
materials used for cell windows.

Sample Handling
• The thickness b of very narrow IR cells can be determined by the

interference fringe method.
• The equation can also be

used to calculate the thickness
of thin polymer films.
• Solid sample must be ground

until its particle size is much
less than the wavelength of
the radiation to avoid the
effects of scattered radiation.

Group Frequencies (3600 to 1250 cm-1)
• Group frequencies and correlation charts serve as a starting

point in the identification process.
The Fingerprint Region (1200 to 600 cm-1)
• Most single bonds give rise to absorption bands at these frequencies;

because their energies are about the same, strong interaction occurs
between neighboring bonds. The absorption bands are thus composites of
these various interactions and depend on the overall skeletal structure of the
molecule.
• Exact interpretation of spectra in this region is seldom possible because of

the complexity of the spectra. However, for identification purposes, the
richness of spectral features is a distinct advantage. Many compounds show
unique absorption bands in this region, which is very useful for final
identification.

Diffuse-Reflectance (DRIFTS) Spectrometry
• Diffuse reflection is a complex process that

occurs when a beam of radiation strikes the
surface of a finely divided powder.
• With this type of sample, specular reflection
occurs at each plane surface. However, because
there are many of these surfaces and they are
randomly oriented, radiation is reflected in all
directions.
• The intensity of the reflected radiation is roughly
independent of the viewing angle.
where R’∞ is the ratio of the reflected intensity of the sample to that of a
nonabsorbing standard, such as finely ground potassium chloride. The quantity
k is the molar absorption coefficient of the analyte, and s is a scattering
coefficient. For a diluted sample, k is related to the molar absorptivity ε and the
molar concentration of the analyte c by the relationship k = 2.303 ε c

Example
• The peak locations are the same in the two spectra but that the relative
peak heights differ considerably.
• The differences are typical, with minor peaks generally appearing larger in
reflection spectra.

Attenuated Total Reflectance (ATR) Spectrometry
• Internal-reflection spectroscopy is a
technique for obtaining IR spectra of
samples that are difficult to deal with,
such as solids of limited solubility,
films, threads, pastes, adhesives,
and powders.
• During the reflection process the

beam penetrates a small distance
into the less dense medium before
reflection occurs. (evanescent wave)
• At wavelengths where the less dense medium absorbs the evanescent

radiation, attenuation of the beam occurs, which is known as attenuated total
reflectance, or ATR.
The penetration depth

Attenuated Total Reflectance (ATR) Spectrometry
• Note that the effective penetration depth can be changed by changing the
crystal material, the angle of incidence, or both. It is possible to obtain a depth
profile of a surface using ATR spectroscopy.
• In practice, a multi-reflection crystal with a 45 degree angle can accommodate

most routine samples.
• One of the major advantages is that absorption spectra are readily obtainable
on a wide variety of sample types with a minimum of preparation.
• Aqueous solutions can also be accommodated provided the crystal is not

water soluble.
• The same bands are observed as in the ordinary absorption spectra but
relative intensities differ.
• ATR band intensity is usually proportional to concentration so that quantitative

measurements can be made.

Advantage of FTIR
• Multiplex gain or the Fellget advantage: In monochromator transmission

measurements only a small fraction of the entire spectrum is observed at a given
time while in FTIR the entire spectrum is observed over the measurement period
of a second or less.
• With N spectral elements, each ∆λ wide, the FTIR has a signal-to-noise

advantage of N1/2 over the monochromator when the detector is limited by noise
other than photon noise. The enhanced signal-to-noise ratio can, of course, be
traded for rapid scanning, with good spectra being attainable in a few seconds in
most cases.
• Interferometric instruments are also characterized by high resolutions (<0.1 cm-1)

and highly accurate and reproducible frequency determinations. It’s helpful when
spectra are to be subtracted for background correction.
• Optical throughput gain or Jacquinot advantage: Referring to the amount of light

one is able to pass through the instrument. Monochromators are limited by the
entrance and exit slits while FTIRs have relatively large entrance apertures. The
optical throughput gain is typically about 100.

Raman Spectrometry
鄭文惠 (Wen-Hui Cheng)
Department of Materials Science and Engineering,

National Cheng Kung University
wcheng@gs.ncku.edu.tw
Academic Year 112 Semester 1

NCKU / MSE
Raman Effect
• Raman spectroscopy is based on the Raman effect first

reported by Raman in 1928.
• If the incident photon imparts energy to the lattice in the

form of a phonon (phonon emission) it emerges as a
lower-energy photon. This down-converted frequency
shift is known as Stokes-shifted scattering.
• In Anti-Stokes-shifted scattering the photon absorbs a

phonon and emerges with higher energy.
Sir Chandrasekhara Venkata Raman

“discovery of the effect of light scattering”
Nobel Prize in Physics for 1930

Raman Effect
• The anti-Stokes mode is much weaker than the Stokes mode and it is Stokes-
mode that is usually monitored.
Raleigh scattering

Raman Theory
When incident light interacts with a molecule, it induces a dipole moment, P, equal to
that of the product of the polarizability α of the molecule and the electric field of the
incident light source. This can be expressed as,
𝑃 = 𝛼𝐸! cos(2π𝜈! 𝑡)
Using the small amplitude approximation, the polarizability can be described as a
linear function of displacement,
𝜕𝛼
𝛼 = 𝛼! + 𝑞 +⋯,
𝜕𝑡 #$!
𝜕𝛼
𝑃 = 𝛼! 𝐸! cos 2π𝜈! 𝑡 + 𝑞! cos(2π𝜈" 𝑡)𝐸! cos(2π𝜈! 𝑡)
𝜕𝑡 #$!
Rayleigh scattering Raman scattering
𝜕𝛼
𝑞! 𝐸! cos[2π 𝜈! − 𝜈" 𝑡 + cos[2π 𝜈! + 𝜈" 𝑡]}
𝜕𝑡 #$!
Stokes Anti-stokes

Raman Spectrum
• For Raman spectra, the abscissa of

is the wavenumber shift, which is
defined as the difference in
wavenumbers (cm-1) between the
observed radiation and that of the
source.
• Note that three Raman lines are

found on both sides of the Rayleigh
lines and that the pattern of shifts
on each side is identical.
• Because the anti-Stokes lines are

λex= 488 nm (𝛎ex = 20,492 cm-1) appreciably less intense than the
corresponding Stokes lines, only
the Stokes part of a spectrum is
generally used.

Raman Spectrum
• It is noteworthy that fluorescence may interfere seriously with the observation of

Stokes shifts but not with anti-Stokes. With fluorescing samples, anti-Stokes
signals may be more useful despite their lower intensities.
• It is important to appreciate that the magnitude of Raman shifts is independent

of the wavelength of excitation.
• It is important to note that the selection rules for Raman scattering require that
there be a change in polarizability during the vibration—that is, ∂α/∂r must be
greater than zero for Raman lines to appear.
• The selection rules also predict that Raman lines corresponding to fundamental
modes of vibration occur with ∆v = ±1. Just as with IR spectroscopy, much
weaker overtone transitions appear at ∆v = ±2.

Raman Theory
A : collection efficiency of the Raman signal

α (ωR,ω) : Raman polarizability of the detected molecule
• From an EM point of view, owing to the small Stokes shift, one usually assumes
that the radiative Stokes field is same as enhancement of the exciting field, thus
the Raman cross section (G) can be expressed by G = 𝐸%&' ( / 𝐸) ( , where 𝐸%&'
is the local field amplitude of the Raman active site and 𝐸) is the field of
incidence.
• The Raman scattering signal can be significantly enhanced if strong electric field
intensity can be introduced – Surface plasmon resonance !
Advanced Characterization of Materials http://bwtek.com/raman-theory-of-raman-scattering/ 8585

Surface-enhanced Raman Scattering (SERS)
The principle of Raman scattering Illustration of SERS sensing
Yohan Lee, et. al., Sensors 17, 1726 (2017)
• A series of experiments in 1977 confirmed that Raman signals can be greatly

increased when molecules are very close to rough metal surfaces or
nanostructures. (The enhancement factor can be as much as ~109 to ~1012)
• It was called surface-enhanced Raman scattering (SERS) or surface-enhanced
Raman spectroscopy

Instrumentation
• Raman scattered light is very weak

(about 1 in 108 parts), Raman
spectroscopy is only practical when an
intense monochromatic light source
like a laser is used.
• The weak scattered light or signal is

passed through a double
monochromator to reject the Raleigh
scattered light and the Raman-shifted
wavelengths are detected by a
photodetector.
• Because the intensity of Raman

scattering varies as the fourth power
of the frequency, argon and krypton
ion sources that emit in the blue and
green region of the spectrum have an
advantage of higher intensity.

Instrumentation
• A major limitation in Raman

spectroscopy is the interference caused Argon ion
by fluorescence, either of impurities or
the sample itself. The fluorescent
background problem is eliminated by
combining Raman spectroscopy with
FTIR.
• The short-wavelength laser sources can

produce significant fluorescence and
cause photodecomposition of the
sample.
• The Nd-YAG source completely

eliminates background fluorescence.

Raman Spectroscopy
• Raman spectroscopy is a vibrational spectroscopic technique that can detect

both organic and inorganic species and measure the crystallinity of solids. For
example, different crystal orientations give slightly different Raman shifts.
• The Stokes line shifts, broadens and becomes asymmetric for microcrystalline Si
with grain sizes below 100Å. The lines become very broad for amorphous
semiconductors.
• By using lasers with varying wavelengths and

hence different absorption depths, it is possible
to profile the sample to some depth. The
technique is non-destructive and requires no
contacts to the sample.
• It is sensitive to strain, allowing it to be used to

detect stress in a semiconductor material or
device with compressive stress giving an
upward and tensile stress a downward shift.

Temperature Effect
514.5nm
Intensity ratio of anti-Stokes to Stokes

lines as a function of temperature. At low T,
there are no thermal phonons available to
be annihilated.

Raman Depolarization Ratios
• In addition to intensity and frequency information, Raman measurements

provide an additional variable that can be useful in determining the structure of
molecules: the depolarization ratio p.
• The depolarization ratio depends on the

symmetry of the vibrations responsible for the
scattering, thus useful in correlating Raman
lines with modes of vibration.
• The 459 cm-1 line for carbon

tetrachloride from a totally
symmetric “breathing”
vibration has depolarization
ratio of 0.005, is thus said to
be polarized.

Raman VS. IR
• Raman scattering results from the same type of quantized vibrational changes
associated with infrared (IR) absorption. Thus, the difference in wavelength
between the incident and scattered visible radiation corresponds to
wavelengths in the mid-IR region.
• Indeed, the Raman scattering spectrum and IR absorption spectrum for a

given species often resemble one another quite closely. Although IR
spectroscopy is still the more widely used vibrational spectroscopic tool, for
several problems, Raman spectroscopy can provide more useful and selective
information.
• Water is quite useful as a solvent in Raman spectroscopy, which is a

tremendous advantage of Raman over IR. In addition, because Raman
scattering is usually measured in the visible or near-IR region, glass or quartz
cells can be used, avoiding the inconvenience of working with sodium chloride
or other atmospherically unstable window materials. Also, the laser source is
easily focused on a small sample.

Raman VS. IR
• The differences between a Raman spectrum and an IR spectrum are not surprising
when it is considered that the basic mechanisms, although dependent on the same
vibrational modes, arise from processes that are mechanistically different.
• IR absorption requires that there be a change in dipole moment or charge

distribution during the vibration. Only then can radiation of the same frequency
interact with the molecule and promote it to an excited vibrational state.
• In contrast, scattering involves a momentary distortion of the electrons distributed

around a bond in a molecule, followed by reemission of the radiation as the bond
returns to its normal state. In its distorted form, the molecule is temporarily
polarized; that is, it develops momentarily an induced dipole that disappears on
relaxation and reemission. Because of this fundamental difference in mechanism,
the Raman activity of a given vibrational mode may differ markedly from its IR
activity.
• Raman spectra are often simpler than IR spectra because the occurrence of
overtone and combination bands is less common in Raman spectra.

Raman VS. IR: Carbon Dioxide
• In the symmetric mode, no change in the dipole moment occurs as the two
oxygen atoms move away from or toward the central carbon atom; thus, this
mode is IR inactive. The polarizability, however, fluctuates in phase with the
vibration because distortion of bonds becomes easier as they lengthen and
more difficult as they shorten. Raman activity is associated with this mode.
• In contrast, the dipole moment of carbon dioxide fluctuates in phase with the
asymmetric vibrational mode. Thus, an IR absorption band arises from this
mode. On the other hand, as the polarizability of one of the bonds increases
as it lengthens, the polarizability of the other decreases, resulting in no net
change in the molecular polarizability. Thus, the asymmetric stretching
vibration is Raman inactive.
• For molecules with a center of symmetry, such as CO2, no IR active

transitions are in common with Raman active transitions. This is often called
the mutual exclusion principle.

Raman VS. IR

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Infrared Spectrometry

鄭文惠 (Wen-Hui Cheng)

Department of Materials Science and Engineering,

Academic Year 112 Semester 1

• The infrared (IR) region of the spectrum encompasses radiation with

• The foundations of modern Fourier Transform Infrared Spectroscopy

Advanced Characterization of Materials 4747

• Note that the horizontal scale

• IR radiation is not energetic enough to bring about the kinds of electronic

• To absorb IR radiation, a molecule must undergo a net change in dipole

• The dipole moment is determined by the magnitude of the charge difference

• If the frequency of the radiation exactly matches a natural vibrational

• The rotation of asymmetric molecules around their centers of mass also

Advanced Characterization of Materials 4949

• No net change in dipole moment occurs during the vibration or rotation of

Advanced Characterization of Materials 5050

• Vibrations fall into the basic

• A stretching vibration involves a

• Bending vibrations are

Advanced Characterization of Materials 5151

The displacement of the molecule can be expressed by using Hook’s law as

𝑚! 𝑚" 𝑑 " 𝑥! 𝑑 " 𝑥"

Advanced Characterization of Materials 5252

The carbonyl stretching band is found experimentally to be in

where h is Planck’s constant, and v is

selection rule states that ∆v = ±1.

Advanced Characterization of Materials 5454

• A molecule containing N atoms have 3N degrees of freedom.

• In defining the motion of a molecule, we need to consider

Advanced Characterization of Materials 5555

Fewer Absorption Bands

(3) The absorption intensity is so low as to be undetectable by ordinary means

More Absorption Bands

Advanced Characterization of Materials 5656

1. Strong coupling between stretching vibrations occurs only when there is

2. Interaction between bending vibrations requires a common bond between

3. Coupling between a stretching and a bending vibration can occur if the

4. Interaction is greatest when the coupled groups have individual energies

5. Little or no interaction is observed between groups separated by two or

6. Coupling requires that the vibrations be of the same symmetry species.

Advanced Characterization of Materials 5757

• C=O stretching vibration, about 1700 cm-1, or 6 μm.

• Experimentally, carbon dioxide exhibits two absorption maxima, one at 2350

• Two stretching vibrations are possible; furthermore, interaction between the

no change in dipole moment a net change in charge distribution

Advanced Characterization of Materials 5858

• The remaining two vibrational modes of carbon dioxide involve scissoring.

Illustrates how IR absorption spectroscopy can sometimes be used

• Coupling of vibrations is a common phenomenon. As a result, the position of

• Although interaction effects may lead to uncertainties in the identification of

Advanced Characterization of Materials 6060

• Three types of instruments for

(1) Dispersive spectrophotometers

(2) FT spectrometers employing

(3) Nondispersive photometers

Advanced Characterization of Materials 6161

• IR sources consist of an inert solid that is heated electrically to a

• The maximum radiant intensity at