SPECTROSCOPY

1. Introduction

Interaction between electromagnetic radiation and matter is studied using spec-

troscopic methods. The study of this interaction as a function of frequency or
wavelength and electromagnetic radiation itself makes spectroscopy a very ver-
satile and powerful tool for the investigation of atomic and molecular structure.
It allows identification of samples, of the determined composition of the samples
(speciation), and of the amount of different species present (quantification), these
being objectives in any analytical procedure. The aspect of quantification in spec-
troscopic methods is called spectrometry. Within the wide range of electromag-
netic radiation, optical spectroscopy conventionally summarizes the ultraviolet
(uv), visible, and infrared (ir) spectral regions. However, it is extended to include
shorter and longer wavelengths that interact with matter by the same basic
mechanism of coupling with the electric vector of the electromagnetic field.
Accordingly, mass, acoustic, particle energy, and magnetic resonance spectro-
scopy are excluded (see MASS SPECTROMETRY; MAGNETIC SPIN RESONANCE).
Spectroscopic techniques can both identify and quantify in a single mea-
surement. Therefore, the identical application of spectroscopy range from
bench analysis of chemical samples in the laboratory over process monitoring
in chemical plants to detection and monitoring of pollutants in the atmosphere,
and as new applications in optical biosensors and chemosensors. All of these will
be discussed in this article. A wide range of compounds can be detected with high
specificity, even in multicomponent mixtures. Many spectroscopic methods are
noninvasive, involving no sample collection, pretreatment, or contamination
(see NONDESTRUCTIVE EVALUATION). Because only optical access to the sample is
needed, instruments can be remotely situated for environmental and process
monitoring using, eg, fiber optics. Spectroscopy provides rapid real-time results,
and allows continuous long-term monitoring. In addition, spectra carry informa-
tion on sample conditions, eg, temperature and pressure.
The many applications of optical spectroscopic methods rely just on a few
basic mechanisms of light–matter interaction, eg, scattering, absorption, and
emission. In spectroscopic analysis, species are identified by the frequencies and
structures of absorption, emission, or scattering features. Since electromagnetic
emission exhibits amplitude, frequency, phase, state of polarization, and time
dependence, all these features can be used to characterize the interaction between
light and matter, and to quantify it by changing the amplitude or intensity.
Absorption (a absorptance, absorption factor), transmision (t transmit-
tance, transmission factor), and reflection (r reflectance, reflection factor) of a
nonscattering and nonfluorescent sample add up to 1 (1):

aþtþr¼1 ð1Þ

According to International Union of Pure and Applied Chemistry (IUPAC)

rules, the terminology for the different quantities in spectroscopy depend on the
units of concentration, on whether the absorbance is decadic or a napierian loga-
rithm, and on the conventions employed in the different spectral regions. In case
of measuring gases and liquids in cells, multiple reflections on the cell walls can

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
2 SPECTROSCOPY Vol. 22

influence the absorptance. For this reason, sometimes an internal absorptance ai

is defined. This happens also in the case of solid samples that cannot be compen-
sated by a nonabsorbing reference sample as is done in the case of liquids or
gasses, for which the reference cell is filled with all components except the one
to be measured. In optical spectroscopy, internal properties are defined to
exclude surface effects and effects of the cuvette, eg, reflexion losses. This
leads to the customary form of the Lambert-Beer-Bouguer law

ftr Itr
¼ ¼ ti ¼ 1
ai ¼ exp ð
kclÞ ð2Þ
f0 I0

The definitions relate to absorbance A10 or Ae using the internal absorp-

tance ai. However, the i in the absorptance a is often omitted. Accordingly, the
decadic absorbance is defined as

A10 ¼
lg ð1
ai Þ ð3Þ

and the napierian absorbance

Ae ¼
ln ð1
ai Þ ð4Þ

Both definitions use absorption coefficients as molar napierian k, as molar (decadic)

e, (linear) decadic a or (linear) napierian a.

A10 Ae a A10 a Ae
a¼ a¼ e¼ ¼ k¼ ¼ ð5Þ
l l c cl c cl

where normally the concentration c is used in mol/dm3, therefore the molar

(decadic) coefficient e, sometimes called the extinction coefficient, has the unit
mol
1 dm3 cm
1. The term ‘‘extinction’’ should properly be reserved for the sum
of the effects of absorption, scattering, and luminescence. In principle, all these
quantities should be used in spectroscopy in terms of spectral intensity I(ne) as a
function of wave number n e, or frequncy n across the spectrum. However, espe-
cially in the visible and uv range wavelength, units of nanometers (nm) [I(l)]
are used instead of frequency. The principles for absorption, fluorescence, and
reflection are shown in Fig. 1.
In practice, deviation from the Bouguer-Lambert-Beer’s law can occur espe-
cially when high concentrations are examined. This deviation might stem from
chemical interactions in the sample, from multiple scattering in the opaque or
inhomogeneous media, or from instrumental effects, eg, insufficient resolving
power or stray light. In part, these deviations can be overcome by calibration
curves that are established if quantified information is desired.
Scattering techniques (2,3) record the change of a usually monochromatic
probe signal scattered by a sample. It can involve elastic (energy-conserving)
interactions, eg, Rayleigh scattering, where photons undergo only a change in
momentum, or the inelastic (energy-changing) Raman effect, in which scattering
is accompanied by discrete changes in frequency. Rayleigh scattering occurs for
Vol. 22 SPECTROSCOPY 3

all species having dimensions much smaller than the wavelength of the probe
light, Mie scattering occurs from larger dielectric particles, and Tyndall scatter-
ing from discontinuities, eg, interfaces. These elastic processes provide little che-
mical information, but in atmospheric applications can furnish a return signal
for laser ir radar (lidar) sounding. The Raman effect is weaker by factors of
103, but spectroscopic analysis of scattered Raman light reveals spectral shifts
characteristic of different chemical species (4–6) (see INFRARED TECHNOLOGY).
Emission spectroscopy is the analysis, usually for elemental composition, of
the spectrum emitted by a sample at high temperature, or that has been excited
by an electric spark or laser. The direct detection and spectroscopic analysis of
ambient thermal emission, usually in the ir or microwave regions, without active
excitation, is often termed radiometry (7). In emission methods, the signal inten-
sity is directly proportional to the amount of analyte present.
Another type of emission is luminescence (8). Fluorescence and phosphores-
cence are types of luminescence, ie, emission attributed to selective excitation by
previously absorbed radiation and chemical reaction rather than to the tempera-
ture of the emitter (9–11). Laser-induced and X-ray fluorescence are important
analytical techniques.
In case of reflection, Lambert cosine law allows us to determine diffuse
reflection as useful in thin-layer chromatography (12) using the Kubelka
Munk function (13). Regular reflection (14) gains increasing interest either to
measure reflectivities as in ellipsometry (15) or interferometric methods (16) or
measuring refractometry based on evanescent field techniques (17). However,
total and regular reflection have their main field of application in the areas of
biochemical and chemical optical sensing (18).
Many schemes for exploiting processes of absorption, emission, and scatter-
ing have been developed around the experimental details of available light
sources, detectors, and spectral analyzers. Spectroscopic analysis has been
strongly impacted by the development of lasers (19,20), used both as powerful
monochromatic excitation sources and as broadly tunable spectroscopic probes
(21–25). Lasers are routinely used both in laboratory analysis and for active
remote sensing (26,27). Their extremely high spectral intensity (photons per
unit bandwidth) and spatial coherence (low divergence, allowing tight focusing)
make even weak scattering processes, eg, the Raman effect, useful. Lasers have
been exploited for many of the newer nonlinear responses (28–31) and for ultra-
sensitivity procedures that allow the detection of single atoms and molecules (32)
(see TRACE AND RESIDUE ANALYSIS). Herein, optical spectroscopy for laboratory ana-
lysis, giving some attention to remote sensing using either active laser-based sys-
tems (33–36) or passive (radiometric) techniques (37–40) is emphasized.
4 SPECTROSCOPY Vol. 22

2. Background

2.1. The Electromagnetic Spectrum. Electromagnetic radiation is

characterized by its wavelength, l, frequency, n, or wavenumber, ne, which are
related in equation 6:

n ¼ c=l ~n ¼ 1=l ¼ n=c ð6Þ

where c is the speed of light. Energy of radiation is related to frequency n or

wavenumber n e. Units for wavelength are commonly nanometers (nm) or micro-
meters (mm) (1 nm ¼ 10 Å ¼ 10
3 mm ¼ 10
9 m); for frequency, some multiple of
cycles per second (hertz); and for wavenumber, reciprocal centimeters (cm
1)
(1 cm
1 & 30 GHz). The photon energy is

E ¼ hn ¼ hc=l ¼ hcne ð7Þ

where h is Planck’s constant, and so is proportional to the frequency and wave-

number (1 eV 8066 cm1).
The electromagnetic spectrum is conventionally divided into several energy
regions characterized by the different experimental techniques employed and the
various nuclear, atomic, and molecular processes that can be studied; these are
summarized in Table 1.
2.2. Atomic and Molecular Energy Levels. Absorption and emission
of electromagnetic radiation can occur by any of several mechanisms. Those
important in spectroscopy are resonant interactions in which the photon energy
matches the energy difference between discrete stationary energy states (eigen-
states) of an atomic or molecular system:

Esystem ¼
Ephoton ¼ hn ð8Þ

This condition is known as the Bohr frequency. Transitions between differ-

ent types of eigenstates have characteristic energies (see Table 1), and so occur in
different spectral regions. All of these regions have at least some applications to
chemical analysis, but the most useful are rotational, vibrational, and electronic
transitions. Molecules and molecular ions exhibit all three types of spectra;
atoms and atomic ions undergo only electronic transitions.
Rotational transitions in gaseous molecules occur in the far-ir and micro-
wave regions, generally l > 100 mm. Very light species absorb at shorter wave-
lengths according to
sffiffiffi
1 f
n¼ ð9Þ
2p m

where f is the force constant, and m the reduced mass (41). In fact, the strong,
dense rotational spectrum of water vapor for l > 15 mm makes operation in fir
difficult. Microwave spectroscopy is an important discipline oriented more
toward molecular structure research than chemical analysis (see MICROWAVE
Vol. 22 SPECTROSCOPY 5

TECHNOLOGY). The radar region, which includes longer microwaves and shorter
radio waves (l  0.54–133 cm), is used for the detection and ranging of extended
objects, from raindrops to aircraft to large weather systems. Microwave and
radio wave spectroscopy is useful for detecting molecules in astronomical sources
(radio astronomy).
Molecules vibrate at fundamental frequencies that are usually in the mid-
ir. Some overtone and combination transitions occur at shorter wavelengths.
Because ir photons have enough energy to excite rotational motions also, the
ir spectrum of a gas consists of rovibrational bands in which each vibrational
transition is accompanied by numerous simultaneous rotational transitions. In
condensed phases, the rotational structure is suppressed, but the vibrational fre-
quencies remain highly specific. Information on the molecular environment can
often be deduced from line widths, frequency shifts, and additional spectral
structure owing to phonon (thermal acoustic mode) and lattice effects.
Shorter wavelength radiation promotes transitions between electronic orbi-
tals in atoms and molecules. Valence electrons are excited in the near-uv or visi-
ble. At higher energies, in the vacuum uv (vuv), inner-shell transitions begin to
occur. Both regions are important to laboratory spectroscopy, but strong absorp-
tion by O2 and O3 make the vuv unsuitable for atmospheric monitoring. Electro-
nic transitions in molecules are accompanied by structure from vibrational and,
in gases, rotational transitions (vibronic and rovibronic bands). Deep inner-shell
electronic transitions can be induced by X-ray excitation, useful for elemental
analysis (see X-RAY TECHNOLOGY). Electronic transitions typically have larger
absorption cross-sections than vibrational transitions, and hence greater analy-
tical sensitivity, but spectral overlap and interferences are more likely to be pro-
blems.
2.3. Transition Widths and Strengths. The widths and strengths of
spectroscopic transitions determine the information that can be extracted from
a spectrum, and are functions of the molecular parameters summarized in
Table 2. Detectivity is determined by spectral resolution and transition strength.
Resolution, the ability to distinguish transitions of nearly equal wavelength,
depends on both the widths of the spectral features and characteristics of the
instrumentation. Unperturbed transitions have natural, DnN, widths owing to
the intrinsic lifetimes of the states involved. The full width at half-maximum
(fwhm), is defined as
nN ¼ ð2ptÞ
1 , where t is the natural lifetime for a sponta-
neous transition in the absence of external perturbations. Natural line widths
can be resolved by modern laser spectroscopies under laboratory conditions.
Natural line widths are broadened by several mechanisms (42). Those effec-
tive in the gas phase include collisional and Doppler broadening. Collisional
broadening results when an optically active system experiences perturbations
by other species. Collisions effectively reduce the natural lifetime, so the broad-
ening depends on a characteristic impact time, tC, that is typically 1 ps at atmo-
spheric pressure:
 
1 1 1

nC ¼ þ ð10Þ
2p t tC
6 SPECTROSCOPY Vol. 22

Doppler broadening arises from the random thermal agitation of the active sys-
tems, each of which, in its own rest frame, sees the applied light field at a differ-
ent frequency. When averaged over a Maxwellian velocity distribution, ie,
assuming noninteracting species in thermal equilibrium, this yields a linewidth
(fwhm) in reciprocal centimeters (cm
1).

ne ¼ 7  16  10
7 ne0 ðT=MÞ
1=2 ð11Þ

where T is the sample temperature in kelvin, M is the molecular weight of the

species in amu, and ne0 is the transition energy in reciprocal centimeters. The
Doppler broadening of a transition represents the fundamental lower limit for
resolution unless special nonlinear spectroscopies are exploited.
Natural and collisional broadening are homogeneous processes because all
radiators experience the same local effects. These produce, for both gases and
liquids, a Lorentzian line shape, with Dn (fwhm) ¼ (2pt0 )
1, where t0 is the effec-
tive lifetime of a radiator’s uninterrupted oscillation period. In gases, this shape
is distorted by Doppler broadening, an inhomogeneous effect having a Gaussian
distribution. The contour of a gas-phase transition is thus the mathematical
combination (convolution) of the Lorentzian and Gaussian functions, the Voigt
profile.
For condensed species, additional broadening mechanisms from local field
inhomogeneities come into play. Short-range intermolecular interactions, includ-
ing solute–solvent effects in solutions, and matrix, lattice, and phonon effects in
solids, can broaden molecular transitions significantly.
Finally, instrumental broadening results from resolution limitations of the
equipment. Resolution is often expressed as resolving power, n/Dn, where Dn is
the probe line width or instrumental bandpass at frequency n. Unless Dn is sig-
nificantly smaller than the spectral width of the transition, the observed line is
broadened, and its shape is the convolution of the instrumental line shape (appa-
ratus function) and the true transition profile.
With inadequate resolution much of the information in a complex spectrum
can be lost leading to consequent degradation of specificity and loss of quantita-
tive accuracy. In condensed phases, demands on instrumental resolution are
modest. In gases at atmospheric pressure, collisional broadening is the dominant
mechanism. There is usually a linear relationship between pressure and line
width such that pressure-broadening coefficients are typically 0.0001–
0.005(cmkPa)
1(0.01–0.5(cmatm )
1) for ir rovibrational transitions. Thus ir
spectrometers used in remote atmospheric sensing might need 0.1 cm
1 resolu-
tion for scanning the troposphere (lower atmosphere), but analysis in the strato-
sphere (> 25 km) may require <0.01 cm
1. Somewhat lower resolution may
suffice for the uv–vis because of larger collisional and Doppler broadening. For
laboratory gas samples, low pressures may be used to obtain the narrowest line
widths. Under these conditions, instrumental resolution becomes an important
consideration. The most advanced techniques of high resolution interferometry
and tunable-laser spectroscopy are required.
The strength of a photon–molecule interaction is determined by the
frequency-dependent cross-section s(n), expressed in centimeters squared (cm2)
Vol. 22 SPECTROSCOPY 7

for absorption and related to a(n) in equation 5; or by the differential cross-

section ds(n)/d in units of cm2/sr for scattering (34). The latter specifies the
likelihood that active species scatter some portion of the incident laser fluence
(photons/cm2) into a viewing solid angle, D, measured in steradians (Fig. 2).
The cross-sections can be expressed as in equation 12:

sðnÞ ¼ s0  Lðn
n0 ;
nÞ ð12Þ

where s0 (or ds0/d) is the peak value for absorption (scattering) and L(n

n0,Dn) is a symmetrical line-shape function parameterized by a center frequency,
n0, and linewidth Dn.
An important semiclassical measure of the frequency-integrated absorption
cross-section, known as Ladenburg’s formula, is equation 13:
Z
sðnÞdn ¼ prc cf ffi Sðcm2  frequencyÞ ð13Þ

where rc is the classical electron radius (2.8  10
13 cm) and f is the oscillator
strength for the transition (43,44). Similar expressions can be written for the dif-
ferential scattering or fluorescence cross-sections (34). The f-values or line
strengths, S, can in principle be calculated from quantum mechanics, but are
generally obtained empirically. The parameter S is related to a matrix element,
dij, connecting the initial and final states of the transition, ie, S / (dij)2, where dij
has dimensions typical of an atom (10
8 cm). The maximum value of the line-
shape function is inversely proportional to the line width, so the peak absorption
(or angle-integrated scattering) cross-sections, s0, can be approximated as in
equation 14:
s0  S=
n ð14Þ

The peak absorption (scattering) cross-sections are thus useful comparative mea-
sures of detectivity because the latter is a product of the line strength and the
practical line resolution.
2.4. General Instrumental Considerations. A spectroscope disperses
light for visual observation, using a slit to define the source, a collimating lens,
a dispersive prism or grating, and an objective lens or telescope. Spectroscopes
fitted with wavelength scales and cameras are termed spectrometers and spec-
trographs, respectively. A monochromator is a spectrometer having an exit slit
in the focal plane to isolate a narrow wavelength region. If the output is focused
on a detector for quantitative intensity measurements it becomes a spectrophot-
ometer. The use of such instrumentation constitutes the field of spectroscopy
(sometimes called spectrometry), although spectroscopes themselves are, as of
the 1990s, of little importance, for the electromagnetic spectrum extends from
10 to 1024 Hz, compared to the visible region of only (3.8–7.5)  1014 Hz.
Selecting suitable materials and components for a very broad frequency
range presents special problems. Front-surface reflecting optics are usually
required because of the lack of suitable achromatic optical materials. Strong
absorption by the atmosphere in many regions requires instrumentation that
8 SPECTROSCOPY Vol. 22

operates in a vacuum or an optical path that can be purged using a transparent

gas. Table 3 indicates components and materials typically used in the important
near-uv, visible, and ir regions.
The principles of the arrangements to measure absorption, transmission,
and reflection are combined in Fig. 3 for various frequency regions.

3. Radio Wave and Microwave Spectroscopy

The longer wavelengths of the electromagnetic spectrum in the microwave range

are used to probe molecular rotation and hyperfine structure (47). A recent
review on the theory and application of microwave spectroscopy to structure
determination is given with an overview of the theory and the microwave spec-
trometers (48). An important application is radio astronomy (49–52), which uses
both radio and microwaves for chemical analysis on galactic and extragalactic
scales. Herein, the terrestrial uses of microwave spectroscopy are emphasize
(53–55). Additional applications can be found in the field of spectrochemical ana-
lysis and for the characterization of quantum dots (56,57).
3.1. Instrumentation. Microwaves have dimensions comparable to
those of the experimental apparatus, so neither geometrical optics nor electrical
circuit theory applies. Analysis by electromagnetic wave theory is required.
Microwave sources are electronic rather than thermal. Klystrons, used most fre-
quently, induce radiofrequency (rf) fields in a resonant cavity using a modulated
electron beam, providing coherent output tunable over a 10% frequency range.
Magnetrons, traveling-wave tubes, and backward-wave oscillators are also use-
ful sources. Klystrons and magnetrons cover 5–50 GHz, but can be tuned into
the submillimeter region using crystal multipliers. No dispersion is required,
because these sources are essentially monochromatic. Microwaves are trans-
mitted through metal waveguides that also serve as gas sample cells. Thin
mica (qv) windows are used when necessary. Detectors are crystal rectifiers
and sometimes bolometers.
3.2. Applications. Molecules couple to an electromagnetic field through
their electric dipoles, so only those having a permanent dipole moment exhibit
significant rotational spectra. For such species, microwave spectroscopy yields
highly precise moments of inertia and details of centrifugal distortion. Applied
electric or magnetic fields induce Stark or Zeeman spectra, respectively. The for-
mer provide the magnitude of the dipole moment. The latter yield its sign and
also the quadrupole moment, a measure of the asymmetry of the molecular
charge cloud. Degeneracies of electron and nuclear spin states can be removed
using applied magnetic fields, revealing energy differences that typically corre-
spond to microwave frequencies. This is the basis of such important techniques
as nuclear magnetic resonance (nmr) and electron paramagnetic resonance (epr)
(also called electron spin resonance, esr), which fall outside the definition herein
of optical spectroscopy. The comparison between microwave and nmr spectro-
scopy in order to attest the utility and importance of the connections between
these two methods is interesting (58).
Microwave spectroscopy is used for studying free radicals and in gas analy-
sis (59). Much laboratory work has been devoted to molecules of astrophysical
Vol. 22 SPECTROSCOPY 9

interest (60). The technique is highly sensitive: 10
12 mol may suffice for a spec-
trum. At microwave resolution, frequencies are so specific that a single line can
unambiguously identify a component of a gas mixture. Tabulations of microwave
transitions are available (61,62). Remote atmospheric sensing (63) is illustrated
by the analysis of trace ClO, O3, HO2, HCN, and N2O at the part per trillion level
in the stratosphere, using a ground-based millimeter-wave superheterodyne
receiver at 260–280 GHz (64). Recent developments in experimental methods
for the study of transient molecules not only in the atmosphere, but also in
laboratories rely also on high resolution spectroscopy of transient molecules
and its application to molecular dynamics (65). These methods compare modern
techniques in conventional and Fourier transform (ft) microwave spectroscopy
(66) and demonstrating ft microwave spectroscopy as an improved tool for inves-
tigation of rotational spectra (67).

4. Infrared Spectroscopy

Infrared spectroscopy has broad applications for sensitive molecular speciation.

Infrared frequencies depend on the masses of the atoms involved in the various
vibrational motions, and on the force constants and geometry of the bonds con-
necting them. Band shapes are determined by rotational structure, and hence by
the molecular symmetry and moments of inertia. The rovibrational spectrum of a
gas thus provides direct molecular structural information, resulting in very high
specificity. A larger number of articles and books cover theory, instrumentation,
and applications (68–71). The vibrational spectrum of any molecule is unique,
except for those of optical isomers. Every molecule, except homonuclear dia-
tomics, eg, O2, N2, and the halogens, has at least one vibrational absorption in
the ir. Several texts treat ir instrumentation and techniques (37,72–74) and
their applications (75–78).
4.1. Instrumentation. The ir region was developed using dispersive
techniques adapted as appropriate from uv–vis spectroscopy. Unfortunately, ir
sources and detectors tend to be inefficient compared to those for other spectral
regions.
In early ir spectrometers (79), mechanically chopped light from a broad-
band source passed through a sample cell, was dispersed by a monochromator
by either refraction in a prism or diffraction from a reflection grating, and con-
verted into an alternating current (ac) electrical signal by a detector. This signal
was amplified with a lock-in amplifier, thus distinguishing the modulated source
beam from thermal ir radiation naturally emitted by the sample. Rotation of the
dispersing element scanned the frequencies across the detector, and proper
mechanical and electrical manipulation yielded a plot of signal intensity versus
wavelength or wavenumber. Highly sophisticated grating spectrophotometers
became available commercially in the 1950s, covering the mid-ir and having
resolutions of 1 cm
1. Many of these instruments employed a double-beam con-
figuration, in which a set of rotating mirrors switched the source beam alter-
nately through the sample and through an equivalent reference path many
times per second. These signals were compared at the detector, and their ratio
10 SPECTROSCOPY Vol. 22

provided a spectrum free from artifacts owing to atmospheric absorption, varia-

tions in source output, and absorption and scattering by cell windows.
Greatly improved performance was achieved using the Fourier transform
spectrometer (fts) (80–82), essentially a Michelson interferometer in which a col-
limated light beam divided by a partially reflecting beam splitter is recombined
after the optical delay (retardation) of one arm is changed by a scanning mirror.
The resulting signal strength as a function of mirror travel is an interferogram,
from which the desired spectrum (intensity vs. wavenumber) can be obtained by
performing a Fourier transform. The discovery of the Cooley-Tukey fast Fourier
transform (fft) algorithm in 1962 and the availability of powerful and inexpen-
sive computers, led to Fourier spectroscopy becoming a practical technique.
There are several reasons for the high performance of Fourier instruments.
Whereas a scanning spectrometer records a spectrum sequentially, one spectral
resolution element at a time, an interferometer processes information from all
frequencies simultaneously giving the multiplex or Fellgett advantage. Inter-
ferometers also have a throughput (Jacquinot) advantage, accepting a large solid
angle of radiation, and hence passing a much greater light flux than can slit-limited
monochromators. These two advantages can be converted into orders-of-magnitude
improvements in resolution, scan time, and/or signal-to-noise (S/N) ratio, the three
related instrumental parameters that are of the greatest practical interest to the
analyst. The resolution of an fts is approximately the reciprocal of the maximum
retardation, or twice the mirror travel. A resolution of 0.1 cm
1 thus requires a
mirror travel of only 5 cm. Many commercial interferometers offer at least this
capability, and research instruments are marketed that can resolve better than
0.002 cm
1. For kinetics studies and monitoring unstable species, scan rates of
50 Hz are available for short mirror travel (low resolution). Step-scan instruments
can achieve nanosecond time resolution (83).
Besides bench and research-grade Fourier transform infrared (ftir) instru-
ments, which have largely replaced dispersive spectrometers, compact and
robust ftir analyzers are available specifically for on-line process monitoring.
Permanently aligned, industrially hardened instruments are vibration- and
shock-resistant and sealed against dust and moisture. Units are available that
can monitor many dozens of gases at less than parts per million sensitivities.
The development of nearly monochromatic lasers that can be continuously
frequency tuned throughout much of the ir (see Table 3) has revolutionized
vibrational spectroscopy (84–86). By far the most used are lead salt semiconduc-
tor tunable diode lasers (TDLs), which can be tuned over 50–100-cm
1 intervals
in continuous scans of >1 cm
1. Commercial TDL systems are modular, consist-
ing of a cryogenic or liquid nitrogen-cooled laser source assembly, collimating
optics, a simple mode-selecting monochromator, and a photodetector with lock-
in amplifier. Because of the limited tuning ranges, TDLs are not suited for gen-
eral survey spectroscopy, but do offer the highest resolution (<0.0003 cm
1). In
addition to continuous tuning, these can be operated at discrete frequencies, tun-
ing on and off a resonance many times per second for instant quantification.
Industrial analytical applications of TDLs include stack-gas monitors for various
pollutants. Other tunable sources, eg, color-center lasers (87), optical parametric
oscillators (OPOs) (88), and far-ir lasers (89,90), are also useful in high resolution
Vol. 22 SPECTROSCOPY 11

spectroscopy. Recently, quantum cascade lasers have been introduced as a

powerful tool (91,92).
4.2. Sampling. Almost any sample can be prepared for ir analysis
(93,94). Cells for gases and liquids, typically 10 cm and 0.1 mm paths, respec-
tively, are available in many configurations. For trace gases, compact small-
volume folded-path cells offer adjustable optical paths up to 200 m (95). Gaseous
species can be isolated in crystal lattices by dilution in an inert gas that is con-
densed at cryogenic temperatures (matrix isolation) (96–98). This eliminates
Doppler and collisional broadening and suppresses rotational structure, concen-
trating all the intensity of a band in one sharp absorption line for increased sen-
sitivity. Solutions and gels can be coated directly on ir-transmitting salt plates or
microporous plastic films (99). Immersion probes are used for in situ analysis in
chemical reaction vessels and process streams.
Solids can be observed directly in thin sections, as mulls in mineral or halo-
carbon oils, as finely ground dispersions in pressed disks of an ir-transparent
salt, eg, KBr, as films cast from solutions, or as solutions in solvents having
few ir absorptions, eg, CCl4 or CS2. Specular reflection from a solid-surface sam-
ples the outer 10 mm of materials, such as coatings (qv) and films. Nonspecu-
larly reflected light is collected by mirrors in diffuse reflectance spectroscopy,
useful for powdered samples and rough surface solids. Examples of such techni-
ques are the characterization of monolayers by specular reflectance (100) and of
catalysts by diffuse reflectance (101). Infrared light can be polarized by wire-grid
or Brewster’s angle pile-of-plates polarizers for the study of oriented and crystal-
line solids (102).
Specialized sampling techniques include ir microscopes that focus down to
10 mm (approximately the ir diffraction limit) for spectra of less than nanogram
samples. This is useful in fiber analysis and forensics (103–106). In attenuated
total reflection (ATR), an ir beam is transmitted inside a thin, highly refractive
crystal (Zn, Se or Ge) by multiple internal reflection; the evanescent wave that
penetrates some fraction of a wavelength into the surrounding lower index med-
ium is absorbed by a sample in optical contact with the crystal, providing a useful
sampling technique for gels, slurries, strongly absorbing liquids, and coatings
(107,108). External reflection methods are also used for solids and films (109).
Spectra of small samples under pressures of up to 100 GPa (106 atm) can be
obtained using diamond anvil cells (110). Many devices have been designed for
holding samples at cryogenic or elevated temperatures (111). Time-resolved tech-
niques are available for the study of transient species (112–114).
For process monitoring and analysis in chemical plants, transmission of the
ir beam through fiber optics allows safe access to a small sample region in harsh
environments far removed from the spectrometer (115–119). Mid-ir transmitting
fibers are available (see Table 3), although usefulness is limited by moisture sen-
sitivity, brittleness, and impurity absorptions. Systems employing low power
diodes and silica fibers have been demonstrated for monitoring explosive gases
and NH3, using near- and mid-ir absorption.
For open-path atmospheric monitoring, the two basic optical arrangements
are point-to-point (bistatic), where the source and detector are separated and the
volume to be sampled lies between them and single-ended (monostatic), in which
a probe beam is returned from a retroreflecting target (a mirror or topographic
12 SPECTROSCOPY Vol. 22

feature) and traverses the sampled volume twice. The optical path length
through the sample may be ill-defined, yielding a column density averaged
over the total path, so results are usually given in units of concentra-
tion  length. Sea-level atmospheric sounding is limited to regions free of H2O
and CO2 absorption. Significant portions of the ir (1.4, 1.9, 2.5–2.9, 4.2–
4.4, 5.5–7.5, and >15 mm) are unusable (120). High altitude observatories and
balloon-borne spectrometers, however, can conduct useful upper atmospheric
and astronomical observations even in the far-ir (89).
4.3. Null-Background Techniques. In conventional absorption spec-
troscopy, the difference between two large quantities, the incident and trans-
mitted intensities, is measured, thus limiting the minimum detectable
absorbance, Amin to 10
3. This can be greatly improved using null-background
techniques, where the detected signal is (within limits) proportional to the source
intensity. An example is harmonic or derivative spectroscopy (84), in which a
narrow-band light source is frequency-modulated and synchronously amplified
at the modulation frequency (or at a nth-order harmonic), yielding the first
(nth-order) derivative of the absorption profile. This eliminates the background,
reduces effects of low frequency drifts in the source, and discriminates against
spurious signals lacking a sharp wavelength dependence at the modulated
frequency. For TDLs, the drive current is modulated using standard rf sources;
balloon-borne TDL spectrometers have reached Amin to  10
5 (121), and labora-
tory values of 10
8 have been reported.
Another such technique is direct calorimetric measurement of the radiant
energy absorbed as the latter is converted into kinetic motion (heat) (4). In photo-
acoustic spectroscopy (pas) (122–125) pressure modulation caused by absorption
of a modulated source is synchronously detected by a sensitive microphone trans-
ducer (spectrophone). A closed gas cell is required (for maximum sensitivity, an
acoustically resonant one), and the microphones used are very small, so pas is
suited for the analysis of small samples. Liquids or solids can be placed in direct
contact with piezoelectric or pyroelectric transducers that convert pressure
waves or temperature changes into an electrical signal. Typical applications of
pas are for opaque solids, highly scattering media, eg, biological specimens,
and low concentration gases, including pollutants (126). The pas detection has
been demonstrated for volatile organics at <ppb levels using line-tunable CO
and CO2 lasers. The parameter Amin can theoretically reach 10
10. Achievable
sensitivity is illustrated by the analysis of ethylene (qv), C2H4, at the 20 parts
per trillion level in air at 10 mm (127).
A closely related technique useful for localized gas concentrations and leaks
is photoacoustic detection and ranging (padar) (128). A laser pulse tuned to an
absorption line generates an acoustic signal that is detected by a parabolic micro-
phone. A range resolution of 1 cm out to 100 m is feasible.
4.4. Applications. Infrared spectroscopy is broadly applicable to analy-
tical problems of molecular speciation and quantification (75,129,130), for most
molecules have strong fundamental vibrational transitions in the mid-ir. In
the region 3–8 mm, many chemical functional moieties exhibit characteristic
group frequencies that are relatively independent of the molecular environment,
providing information on the chemical nature of the absorber (131,132). An
example is the strong C – O stretching mode in saturated aliphatic ketones at
Vol. 22 SPECTROSCOPY 13

1705–1725 cm
1 (see KETONES). At longer wavelengths, the frequencies are influ-
enced more by the skeletal vibrations of the molecule. This is known as the fin-
gerprint region where even similar species may have sufficiently different
spectra to be readily distinguished.
Single-component unknowns can be identified by simply comparing their
spectra with reference spectra, of which many catalogs are available (133). Refer-
ence spectra are also available in digitized versions, and searches of databases
(qv) can be made rapidly by computer. Even if no reference spectrum of the
unknown is available, the group frequencies may provide enough information
for an experienced spectroscopist to make a full identification. The rovibrational
structure in gaseous samples further increases specificity, and also furnishes an
estimate of the sample temperature that may be useful in remote sensing.
Mixtures can be identified with the help of computer software that sub-
tracts the spectra of pure compounds from that of the sample. For complex mix-
tures, fractionation may be needed as part of the analysis. Commercial
instruments are available that combine ftir, as a detector, with a separation tech-
nique, eg, gas chromatography (gc), high performance liquid chromatography
(hplc), or supercritical fluid chromatography (134,135). Instruments, eg, gc/ftir,
are often termed hyphenated instruments (136). Pyrolyzer (137) and thermo-
gravimetric analysis (tga) instrumentation can also be combined with ftir for
monitoring pyrolysis and oxidation processes (138) (see ANALYTICAL METHODS,
HYPHENATED INSTRUMENTS).
Quantitative analysis based on Beer’s law (eq. 1) is performed by measuring
the absorption at a peak of known strength. In n-component mixtures, n such
features are measured and the resulting set of simultaneous linear equations
is solved for the n concentrations. Detection limits depend on the intrinsic
band strengths, the optical configuration employed (especially the path length),
and the spectral resolution. For solutions, these are typically in the range of 0.1–
1%, with precisions of a few percent of the quantity measured. For narrow
absorptions, sensitivity improves with increasing resolution until the latter
becomes somewhat less than the absorption width. Tunable lasers, because of
their narrow line widths and easy adaptability to derivative detection, provide
excellent sensitivity. Low power TDLs monitoring sharp rovibrational lines in
gaseous samples can detect molecules at the ppb level at atmospheric pressures
over a single-pass 10-cm path length.
The ir spectral region is particularly useful for organic compounds, which
have sufficiently distinctive spectra to be easily identified and quantified.
Areas of application include drug analysis (139), biological systems (140–142),
surface analysis (143), isotopic analysis (144), polymers (145,146), and electrode
processes in solutions (spectroelectrochemistry) (147). Infrared remote sensing
can be as varied as monitoring volatile organics in indoor air by ftir (148), ethy-
lene emissions from a petrochemical plant at the ppb level using a monostatic
CO2 laser system (149), general atmospheric monitoring with TDLs (150),
and upper atmospheric studies using airborne ftir (151,152) (see AIR POLLUTION;
INFRARED TECHNOLOGY). Novel applications are known in biology (153) and clinical
medicine (154).
4.5. Near-Infrared Spectroscopy. Many vibrational overtones and
combinations, especially of hydrogen-containing functional groups, appear in
14 SPECTROSCOPY Vol. 22

the near-infrared (nir). Although these bands are broad and weak, transmission
and reflection nir spectroscopies have emerged as important probes for industrial
and process analysis (155–159), eg, monitoring moisture, saturation of oils, and
protein and fat content in the food and agricultural industries. The nir radiation
can probe, with minimal sample preparation, long-path, concentrated, and aqu-
eous samples that would totally absorb longer wavelengths. The potential loss of
sensitivity is offset by instrumental advantages, eg, dependable low cost tunable
laser sources, sensitive detectors, and fiber optics suitable for industrial environ-
ments. Usually, grating or ftir spectrometers are used, but low resolution band-
pass filters may suffice. Filters can be either fixed-frequency interference or
tunable acoustooptic (160,161). Because nir bands often overlap, chemometric
techniques (162–164) are useful in data reduction (see CHEMOMETRICS).
Solid-state multielement detector arrays in the focal planes of simple grat-
ing monochromators can simultaneously monitor several absorption features.
These devices were first used for uv–vis spectroscopy. Infrared coverage is lim-
ited (see Table 3), but research continues to extend the response to longer wave-
lengths. Less expensive nir array detectors have been applied to on-line process
instrumentation (165) (see PHOTODETECTORS).
Examples of nir analysis are polymer identification (166,167), pharmaceu-
tical manufacturing (168), gasoline analysis (169,170), and on-line refinery pro-
cess chemistry (171). The nir fiber optics have been used as immersion probes for
monitoring pollutants in drainage waters by attenuated total internal reflectance
(172). The usefulness of nir for aqueous systems has led to important biological
and medical applications (173). Interesting applications in spectroelectrochemis-
try are published (174).
4.6. Far-Infrared Spectroscopy. In this wavelength range of 1000–
100 mm and in the frequency range of 1011 –1012 Hz (‘‘terahertz’’ range), rota-
tional transitions of polar molecules in the gas phase as well as vibrational
modes of crystals and biological macromolecules are examined (175–177).
Another application is measurement of hydrogen bonds, especially in matrices.
Furthermore, single- and double-strand DNA could be discriminated, therefore
terahertz spectroscopy is a potential application for genomics (178). Quantum
dots are also characterized (179). It can also be used in environmental pollution
control, therefore this method is considered as having high potential for the
future.
4.7. Radiometry. Radiometry is the measurement of radiant electro-
magnetic energy (37,38,180), considered herein to be the direct detection and
spectroscopic analysis of ambient thermal emission, as distinguished from tech-
niques in which the sample is actively probed. At any temperature above abso-
lute zero, some molecules are in thermally populated excited levels, and
transitions from these to the ground-state radiate energy at characteristic fre-
quencies. From Wien’s displacement law, lmaxT ¼ 2898 mmK, the emission max-
imum at 300 K is near 10 mm in the mid-ir. This radiation occurs at just the
energies of molecular rovibrational transitions, so thermal emission carries
much the same information as an ir absorption spectrum. Detection of the emis-
sions of remote thermal sources is the ultimate passive and noninvasive techni-
que, requiring not even an optical probe of the sampled volume.
Vol. 22 SPECTROSCOPY 15

When the spectral characteristics of the source itself are of primary inter-
est, dispersive or ftir spectrometers are readily adapted to emission spectroscopy.
Commercial instruments usually have a port that can accept an input beam
without disturbing the usual source optics. Infrared emission spectroscopy at
ambient or only moderately elevated temperatures has the advantage that no
sample preparation is necessary. It is particularly applicable to opaque and
highly scattering samples, anodized and painted surfaces, polymer films, and
atmospheric species (181). The Voyager interferometric spectrometer (IRIS) spec-
tra from the outer planets demonstrated the analytical capabilities of ftir emis-
sion spectroscopy. As an example of industrial monitoring, smokestack effluents
have been analyzed by ftir at a range of 74 m, using H2O/CO2 concentration
ratios to distinguish gas and oil combustion (182). Field-deployable commercial
instruments achieve sensitivities of the order of ppmm out to 1 km using retro-
reflectors.
Direct analysis of weak ambient thermal radiation in the presence of an
intense solar background is difficult. A sensitive technique for detecting these
signals is laser heterodyne radiometry, in which one measures not the emitted
frequency itself, but the beat frequency between this and another, accurately
known, frequency. The incident radiation is combined with the output of a coher-
ent local oscillator (LO), usually a fixed-frequency laser, in a high speed photo-
mixer, thus generating a difference frequency called the intermediate frequency
(IF), which is synchronously detected and amplified. The IF preserves the spec-
tral characteristics of the source, but shifts this information into the rf region,
where sensitive radio detection techniques can be used. The tuning range is lim-
ited by the IF bandwidth of the mixer. The HgCdTe photodiodes used in the ir
provide a spectrum covering 0.08 cm
1 around the LO frequency. The require-
ment of finding a molecular transition this close to a gas laser frequency is highly
restrictive, so the technique is not suitable for speciation, but rather for monitor-
ing one or a few specific molecular features. Tunable diode lasers have sufficient
power to serve as local oscillators, permitting continuous tunability, but any sin-
gle TDL is limited to a tuning range of some 100 cm
1. Heterodyne radiometry
provides excellent sensitivity, and has been used with appropriate receiving tele-
scopes for detection of constituents of planetary and stellar atmospheres.

5. Molecular Uv–Vis Absorption Spectroscopy

Spectroscopy in the uv–vis detects electronic transitions, and so is applicable to

both atoms and molecules. This is a mature technique having important qualita-
tive and quantitative applications (183–187).
5.1. Instrumentation and Sampling. Quartz spectrographs and photo-
graphic plates long served for the near-uv–vis–nir region (188), but modern com-
mercial recording instruments employ holographic gratings and photomultiplier
tubes or (in the nir) avalanche photodiode detectors to cover  190 nm–3 mm (see
HOLOGRAPHY; PHOTODETECTORS). A typical benchtop spectrophotometer has 2-nm
resolution in the uv–vis, but dual-grating research instruments can resolve
0.05 nm. In the vacuum ultraviolet (vuv), special techniques are required
(189–191). Molecular oxygen absorbs below 190 nm , and below the transmission
16 SPECTROSCOPY Vol. 22

limit of lithium fluoride, LiF (105 nm), no bulk optical materials are suitable,
even as window materials. This specialized region is not used for routine chemi-
cal analysis.
Simple uv–vis monochromators are widely used with solid-state imaging
arrays (192,193), called optoelectronic imaging devices (OIDs) or optical multi-
channel analyzers (OMAs), placed in the focal plane to record a spectrum nearly
instantaneously. These are the modern equivalent of the photographic plate, and
have the advantage over an emulsion of rapid response and real-time results. An
array detector consists of a set of photodiodes together with an integral electronic
readout scheme. Arrays having time-gated windows as short as 5 ns are useful
for spectroscopy and kinetics of short-lived and unstable species, for which
arrays have obvious advantages over mechanically scanned spectrophotometers,
and are often superior to fts. Two-dimensional (2D) arrays designed for image
recording can be used for time-resolved spectroscopy by rastering a temporally
changing spectrum across the second dimension of the array. Modern routine
spectrometers use charge-coupled devices (CCD) (194,195) as detection elements
that provide wavelength resolutions even below 1 nm in dependence on the grat-
ing used and repetition times of a few milliseconds. Even CMOS technology (196)
is coming up as a modern substitute for photoplates, enabling fast recording
times and high resolution. Such cameras have made uv–vis spectroscopy a
very interesting method and suitable for many applications. A recent review
compares photodetectors (197).
Interferometry is difficult in the uv because of much greater demands on
optical alignment and mechanical stability imposed by the shorter wavelength
of the radiation (198). In principle, any fts interferometer can be operated in
the uv when the proper choice of source, beam splitter, and detector is made,
but in practice good performance at wavelengths much shorter than the visible
has proved difficult to obtain. Some manufacturers have claimed operating limits
of 185 nm, and ft laboratory instruments have reached 140 nm (191). More low
priced results are obtained using diode array spectrometers that use the above
mentioned CCD devices and a so-called polychromator (a monochromator with-
out an exit slit), which allows monitoring of many wavelenghts in parallel on the
diode array (199).
Tunable uv–vis lasers are well developed (21). Optically pumped organic
dye lasers provide especially useful continuously tunable high power sources,
widely used in laboratory research on spectroscopy and photochemistry (see
PHOTOCHEMICAL TECHNOLOGY SURVEY). A single output frequency is selected from
the broad-band fluorescence by a dispersive optical cavity. Pulsed dye lasers,
pumped with fixed-frequency Nd:YAG, excimer, or Cu-vapor lasers, or by flash-
lamps, can provide high peak powers at repetition rates to 100 Hz and line
widths of 0.1–1 cm
1, which can be improved to <0.01 cm
1 with an intracavity
etalon (a pair of parallel plates acting as an interferometer). A given dye–solvent
combination can typically be tuned continuously over a 40–80-nm range. Using
Arþ or Krþ pump lasers, continuous wave (cw) operation is possible having out-
put powers of 0.1–1 W. Multimode cw cavities can achieve line widths of a few
gigahertz, and commercial ring-laser geometries improve the resolution to
<0.5 MHz over a 1-cm
1 continuous scan. Dye lasers have certain drawbacks.
These are complex devices requiring a separate pump laser (or at least a flashlamp)
Vol. 22 SPECTROSCOPY 17

and having demanding optical and alignment requirements, especially the syn-
chronization of the tuning elements. Moreover, dye lasers usually require a flow-
ing dye system (for cw operation, a liquid dye jet) to dissipate heat generated by
the pump. Other useful laser sources are available (see Table 3), including con-
version of longer wavelength tunable lasers by Raman shifting or by frequency
doubling in nonlinear media.
Most of the specialized ir sampling methods described have uv equivalents
with appropriate modifications. Sample cells (cuvettes) for solutions, typically of
1-cm path lengths, may be of glass or quartz, and are available for sample
volumes as small as a few microliters. There is a wide choice of suitable solvents,
including (for l > 200 nm) water and most saturated organic compounds. Differ-
ence spectroscopy with double-beam instruments is used in the uv–vis not only
to eliminate background effects, but to assess the effects of changes in pH, tem-
perature, or solvent on one of two otherwise identical samples. Specialized hard-
ware allows the direct scanning of electrophoresis gels and films. Derivative
spectroscopy (200,201) by either numerical differentiation or beam modulation
methods is important in determining absorbances of weak features obscured
by stronger peaks. Photoacoustic methods are employed for strongly absorbing
samples. Glass and polymer fiber optics are available for process monitoring.
5.2. Applications. Ultraviolet–visible absorption results from transi-
tions between outer-electron shells. The specific moiety or structure responsible
is termed the chromophore. Compounds having only single C
O bonds generally
absorb only in the vuv. Saturated organic compounds containing heteroatoms
exhibit uv transitions, and the p electrons of an unsaturated bond or aromatic
nucleus are strong chromophores, absorbing more strongly and at longer wave-
lengths (to the visible) in conjugated and fused-ring systems. Inorganic species
having incomplete electron shells, notably transition-metal cations, also absorb
in the uv–vis.
The uv–vis spectra do not offer the unique group frequencies and finger-
printing ability of the ir, but different chromophores exhibit absorptions at spe-
cific wavelengths, l, and have characteristic intensities. These are tabulated in
handbooks as lmax and Emax, where Emax is a molar decadic absorption coefficient
equivalent to the a(n) of equation 1, but in units typically of L/(molcm). Thus the
ketone C – O has a strong absorption at 195 nm and a much weaker one at 270–
285 nm. Spectral atlases and cataloges are available (202–204), as are specialized
treatments of laboratory analysis in such fields as pharmaceuticals (qv) (205,206)
and biomedical diagnostics (207) . Scanning uv–vis diode-array absorption detec-
tors are used in hplc, and can cover 190–600 nm in 0.1 s using a 10-mL sample.
The instrumentation is reviewed in Ref. 208, curve-fitting techniques are dis-
cussed (209,210), and various detectors are compared (211). In addition, a com-
parison with nuclear magnetic resonance (nmr) is possible (212).
Photon energies sufficient to promote electronic transitions can also excite
vibrational and rotational transitions, so the electronic spectra of gaseous mole-
cules consist of highly structured rovibronic bands, having very high specificity.
In condensed phases, rotational structure is suppressed, but the molecules still
vibrate, resulting in vibronic bands with progressions of characteristic vibra-
tional frequencies that accompany each electronic transition. The uv offers
high sensitivity and excellent quantitative accuracy. The greater uv absorption
18 SPECTROSCOPY Vol. 22

cross-sections (see Table 2) and more efficient uv sources and quantum detectors
result in detection limits several orders of magnitude better than in the ir. On
the other hand, spectroscopic congestion may be a problem. Many strong transi-
tions occur in a relatively narrow wavelength region. Spectral overlap, and the
greater susceptibility of shorter wavelength radiation to Rayleigh and particu-
late scattering and turbulence, limits the use of uv spectroscopy for identifying
complex mixtures in process streams or in the atmosphere.
Atmospheric and remote-sensing applications of uv–vis spectroscopy have
been reviewed (213,214). Many volatile organics absorb in the near-uv, and the
vapors exhibit rovibronic structure suitable for identification and quantification
if interferences can be avoided. Especially suitable for uv monitoring are the
strong Huggins (300–370 nm) and Hartley (210–300 nm) bands of O3; other inor-
ganics, eg, NO2 and SO2, have been successfully analyzed at kilometer distances
(see OZONE).
The main application of uv–vis spectrometry is to examine liquid or gas
samples in routine analysis. The techniques, instrumentation and data handling
are described in (186,215–217). Detection of uv–vis is typical in chromatography,
either liquid or tlc; furthermore it is a basis of optical sensors being either
optrodes (218) or using fluorescence or reflectance. In past years, the optical sen-
sors have been reviewed frequently (219–221).

BIBLIOGRAPHY

‘‘Spectroscopy, Optical’’ in ECT 4th ed., Vol. 22, pp. 627–670, by R. S. McDowell and J. F.
Kelly, Pacific Northwest National Laboratory; ‘‘Spectroscopy, Optical’’ in ECT (online),
posting date: December 4, 2000, by R. S. McDowell and J. F. Kelly, Pacific Northwest
National Laboratory.

CITED REFERENCES

1. I. Mills and co-workers, eds., Quantities, Units and Symbols in Physical Chemistry,
Blackwell Science, 1993, p. 32.
2. H. C. van der Hulst, Light Scattering by Small Particles, John Wiley & Sons, Inc.,
New York, 1957.
3. M. L. Mishchenko, L. D. Travis, and A. A. Lacis, Scattering, Absorption, and Emis-
sion of Light by Small Particles, Cambridge University Press, 2002, p. 462.
4. J. D. Ingle, Jr., and S. R. Crouch, Analytical Spectroscopy, Prenctice-Hall, Engle-
wood Cliffs, N.J., 1988.
5. S. Wartewig, IR and Raman Spectroscopy: Fundamental Processing, John Wiley &
Sons, Inc., Chichester, U.K., 2002, p. 250.
6. E.-H. Korte, H. Takahashi, and J. Laane, J. Mol. Struct., 657 (2003).
7. H. Freiser and G. H. Nancollas, Compendium of Analytical Nomenclature, 2nd ed.,
International Union of Pure and Applied Chemistry, Analytical Chemistry Division,
1987.
8. C. A. Parker, Photoluminescence of Solutions, Elsevier, London, 1968.
Vol. 22 SPECTROSCOPY 19

9. M. Hof, R. Hutterer, and V. Fidler, eds., Fluorescence Spectroscopy in Biology:

Advances Methods and Their Applications to Membranes, Proteins, DNA, and Cells,
Springer Series Fluorescence, Springer GmbH, Berlin, 2005, p. 305.
10. M.-A. Myek and B. W. Pogue, eds., Handbook of Biomedical Fluorescence, Marcel
Dekker Inc., New York, 2003, p. 665.
11. B. Valeur, ed., Molecular Fluorescence—An Introduction: Principles and Applica-
tions, 1st ed., Wiley-VCH, Weinheim, 2000, p. 250.
12. R. Kellner, J.-M. Mermet, M. Otto, and H. M. Widmer, Analytical Chemistry, Wiley
VCH, Weinheim, 1998, p. 204.
13. P. Kubelka, J. Opt. Soc. Am. 38, 448 (1948).
14. N. J. Harrick, Internal Reflection Spectroscopy, Harrick Scientific Corporation,
New York, 1979.
15. R. M. A. Azzaam and N. M. Bashara, Ellipsometry in Polarized Light, North Holland
Amsterdam, 1988.
16. E. Hecht and A. Zajac, Optics, Addison-Wesley, Reading, 1974.
17. M. Born and E. Wolf, Principles of Optics, Pergamon, New York, 1980.
18. G. Gauglitz, Anal Bioanal Chem. 381(1), 141 (2005).
19. P. W. Milonni and J. H. Eberly, Lasers, John Wiley & Sons, Inc., New York, 1988.
20. J. Hecht, The Laser Guidebook, 2nd ed., TAB Books, Blue Ridge Summit, Pa., 1992.
21. W. Demtröder, Laser Spectroscopy: Basic Concepts and Instrumentation, 2nd ed.,
Springer-Verlag, Berlin, 1996.
22. D. S. Kliger, ed., Ultrasensitive Laser Spectroscopy, Academic Press, Inc., New York,
1983.
23. J. R. Murray, in L. J. Radziemski, R. W. Solarz, and J. A. Paisner, eds., Laser Spec-
troscopy and Applications, Marcel Dekker, Inc., New York, 1987, pp. 91–174.
24. D. L. Andrews, ed., Applied Laser Spectroscopy: Techniques, Instrumentation, and
Applications, VCH Publishers, New York, 1992.
25. E. R. Menzel, Laser Spectroscopy: Techniques and Applications, Marcel Dekker, Inc.,
New York, 1995.
26. D. Meschede, Optics, Light and Lasers: An Introduction to the Modern Aspects of
Laser Physics, Optics and Photonics, John Wiley & Sons, Inc., Chichester, U.K.,
2003, p. 430.
27. C. E. Webb and J. D. C. Jones, eds., Handbook of Laser Technology and Applications,
Vols. 1,2,3, IOP, Bristol, U.K., 2003.
28. M. D. Levenson and S. S. Kano, Introduction to Nonlinear Laser Spectroscopy, rev.
ed., Academic Press, Inc., Boston, Mass., 1988.
29. S. Mukamel, Principles of Nonlinear Optical Spectroscopy, Oxford University Press,
New York, 1995.
30. N. Bloembergen, Nonlinear Optics, 4th ed., World Scientific Publishing Co., River
Edge, N.J., 1996.
31. R. L. Sutherland, Handbook of Nonlinear Optics, Marcel Dekker, Inc., New York,
1996.
32. B. L. Fearey, Adv. Opt. Methods Ultrasensitive Detection, SPIE Proc. 2385 (1995).
33. E. D. Hinkley, ed., Laser Monitoring of the Atmosphere, Springer-Verlag, Berlin,
1976.
34. R. M. Measures, Laser Remote Sensing, John Wiley & Sons, Inc., New York, 1984.
35. R. M. Measures, ed., Laser Remote Chemical Analysis, John Wiley & Sons, Inc.,
New York, 1988.
36. W. B. Grant, J. R. Murray, in L. J. Radziemski, R. W. Solarz, and J. A. Paisner, eds.,
Laser Spectroscopy and Applications, Marcel Dekker, Inc., New York, 1987,
pp. 565–621.
20 SPECTROSCOPY Vol. 22

37. J. T. Houghton, F. W. Taylor, and C. D. Rodgers, Remote Sounding of Atmospheres,

Cambridge University Press, Cambridge, U.K., 1984.
38. R. Beer, Remote Sensing by Fourier Transform Spectrometry, John Wiley & Sons,
Inc., New York, 1992.
39. K. Narahari Rao and A. Weber, eds., Spectroscopy of the Earth’s Atmosphere and
Interstellar Medium, Academic Press, Inc., Boston, Mass., 1992.
40. J. Ballard, Adv. Spectrosc. 24, 149 (1995).
41. I. Mills and co-eds., Quantities, Units and Symbols in Physical Chemistry, Blackwell
Science, 1993, p. 25.
42. G. Gauglitz and D. S. Moore, Pure Appl. Chem. 71, 2189–2204 (1999).
43. A. C. G. Mitchell and M. W. Zemansky, Resonance and Radiation and Excited
Atoms, Cambridge University Press, Cambridge, U.K., 1971.
44. J. T. Houghton and S. D. Smith, Infra-Red Physics, Oxford University Press, Oxford,
U.K., 1966.
45. H. Naumer, W. Heller, and G. Gauglitz, eds., Untersuchungsmethoden in der
Chemie, Wiley-VCH, Weinheim, 2003.
46. D. A. Skoog and J. J. Leary, Principles of Instrumental Analysis, Saunders College
Publishing, Fort Worth, Tex., 1992.
47. N. Fitzgerald, Spectroscopy 15(6), 40 (2000).
48. H. Mollendal, Mathematics, Physics and Chemistry, NATO Science Series II, Vol. 68,
2002, pp. 11–29.
49. J. D. Kraus, Radio Astronomy, 2nd ed., Cygnus-Quasar Books, Powell, Ohio, 1986.
50. G. L. Verschuur and K. I. Kellermann, eds., Galactic and Extragalactic Radio
Astronomy, 2nd ed., Springer-Verlag, New York, 1988.
51. K. Rohlfs and T. L. Wilson, Tools of Radio Astronomy, 2nd ed., Springer-Verlag,
New York, 1996.
52. B. F. Burke and F. Graham-Smith, An Introduction to Radio Astronomy, Cambridge
University Press, New York, 1996.
53. C. H. Townes and A. L. Schawlow, Microwave Spectroscopy, McGraw-Hill Book Co.,
Inc., New York, 1955; corrected reprint, Dover, New York, 1975.
54. G. W. Chantry, ed., Modern Aspects of Microwave Spectroscopy, Academic Press,
London, 1979.
55. W. Gordy and R. L. Cook, Microwave Molecular Spectra, 3rd ed., John Wiley & Sons,
Inc., New York, 1984.
56. R. H. Blick, in H. S. Nalwa, ed., Handbook of Nanostructured Materials and Nano-
technology, Academic Press, San Diego, Calif., 2000.
57. R. H. Blick, A. W. Holleitner, and H. Qin, in J. P. Bird, ed., Electron Transport in
Quantum Dots, Kluwer Academic Publishers, Norwell, Mass., 2003.
58. D. L. Bryce and R. E. Wasylishen, Acc. Chem. Res. 36(5), 327334 (2003).
59. R. Varma and L. W. Hrubesh, Chemical Analysis by Microwave Rotational Spectro-
scopy, John Wiley & Sons, Inc., New York, 1979.
60. S. Saito, Appl. Spectrosc. Rev. 25, 261 (1989–1990).
61. P. F. Wacker and P. Kisliuk, eds., Microswave Spectral Tables, Vol. 1, National
Bureau of Standards, Washington, D.C., 1964–1969.
62. F. J. Lovas, Frequencies for Interstellar Molecular Microwave Transitions, Physics
Laboratory, National Institute of Standards and Technology, Gaithersburg, Md.,
1996; on Internet at http:\\[Link].
63. M. A. Janssen, ed., Atmospheric Remote Sensing by Microwave Radiometry, John
Wiley & Sons, Inc., New York, 1993.
64. A. Parrish, R. L. deZafra, P. M. Solomon, and J. W. Barrett, Radio Sci. 23, 106
(1988).
65. E. Hirota and Y. Endo, Adv. Ser. Phys. Chem. 9, 1 (1997).
Vol. 22 SPECTROSCOPY 21

66. R. D. Suenram and A. M. Andrews, Exp. Methods Phys. Sci. 29B, 273 (1996).
67. H. Dreizler, Ber. Bunsengesellschaft 99(12), 1451 (1995).
68. V. P. Tolstoy, I. Chernyshova, and V. A. Skryshevsky, Handbook of Infrared Spectro-
scopy of Ultrathin Films, John Wiley & Sons, Inc., 2003.
69. B. H. Stuart, Infrared Spectroscopy, John Wiley & Sons, Inc., New York, 2004.
70. X. P. V. Maldague, Theory and Practice of Infrared Technology for Nondestructive
Testing, John Wiley & Sons, Inc., New York, 2001.
71. J. Demaison, NATO Sci. Ser., II: Math., Phys. Chem. 68, 31 (2002).
72. H. A. Willis, J. H. van der Maas, and R. G. J. Miller, eds., Laboratory Methods in
Vibrational Spectroscopy, 3rd ed., John Wiley & Sons, Inc., New York, 1987.
73. I. J. Spiro and M. Schlessinger, Infrared Technology Fundamentals, 2nd ed., Marcel
Dekker, Inc., New York, 1995.
74. W. L. Wolfe, Introduction to Infrared System Design, SPIE Press, Bellingham,
Wash., 1996.
75. A. L. Smith, Applied Infrared Spectroscopy: Fundamentals, Techniques, and Analy-
tical Problem-Solving, John Wiley & Sons, Inc., New York, 1979.
76. N. B. Colthup, L. H. Daly, and S. E. Wiberly, Introduction to Infrared and Raman
Spectroscopy, 3rd ed., Academic Press, Inc., Boston, Mass., 1990.
77. M. Diem, Introduction to Modern Vibrational Spectroscopy, John Wiley & Sons, Inc.,
New York, 1993.
78. B. Schrader, Infrared and Raman Spectroscopy: Methods and Applications, VCH
Publishers, New York, 1994.
79. F. A. Miller, Anal. Chem. 64, 824A (1992); P. A. Wilks, Jr., Anal. Chem. 833A
(1992); P. R. Griffiths, Anal. Chem. 868A (1992); N. Sheppard, Anal. Chem.
877A (1992).
80. J. R. Ferraro and L. J. Basile, eds., Fourier Transform Infrared Spectroscopy,
Vols. 1–4, Academic Press, Inc., New York, 1978–1985.
81. P. R. Griffiths and J. A. de Haseth, Fourier Transform Infrared Spectroscopy, John
Wiley & Sons, Inc., New York, 1986.
82. J. R. Ferraro and K. Krishnan, eds., Practical Fourier Transform Infrared Spectro-
scopy: Industrial and Laboratory Chemical Analysis, Academic Press, Inc., San
Diego, Calif., 1990.
83. R. A. Palmer, Spectroscopy 8(2), 26 (Feb. 1993).
84. C. Webster, R. Menzies, and E. D. Hinkley, in Ref. 34, pp. 1987–1991.
85. R. Grisar and co-workers, eds., Monitoring of Gaseous Pollutants by Tunable Diode
Lasers, 3 Vols., Kluwer Academic Publishers, Boston, Mass., 1987–1991.
86. R. S. McDowell, Vib Spectra Struct 10, 1 (1981).
87. L. F. Mollenauer, in L. F. Mollenauer and J. C. White, eds., Tunable Lasers,
Springer-Verlag, Berlin, 1987.
88. U. Simon and F. K. Tittel, Laser Focus World 30(5), 99 (May 1994).
89. G. A. Blake and co-workers, Rev. Sci. Instrum. 62, 1693 (1991).
90. K. M. Evenson, in G. W. F. Drake, ed., Atomic, Molecular, & Optical Physics Hand-
book, American Institute of Physics, Woodbury, N. Y., 1996, pp. 473–478.
91. L. Hvozdara and co-workers, Vib Spec 30(1), 53 (2002).
92. C. Charlton, A. Katzir, and B. Mizaikoff, Analytical Chemistry, web-released June 9,
2005.
93. P. B. Coleman, ed., Practical Sampling Techniques for Infrared Analysis, CRC
Press, Boca Raton, Fla., 1993.
94. T. J. Porro and S. C. Pattacini, Spectroscopy 8(7), 40 (Sept. 1993); 8(8), 39 (Oct. 1993).
95. J. Altmann, R. Baumgart, and C. Weitkamp, Appl. Opt. 20, 995 (1981).
96. E. L. Wehry and G. Mantov, Prog. Anal. Spectrosc. 10, 507 (1987).
22 SPECTROSCOPY Vol. 22

97. M. J. Almond and A. J. Downs, Spectroscopy of Matrix Isolated Species, John Wiley
& Sons, Inc., New York, 1989; Adv. Spectrosc. 17 (1989).
98. N. K. Wilson and J. W. Childers, Appl. Spectrosc. Rev. 25, 1 (1989).
99. T. A. Dirkson and J. E. Gagnon, Spectroscopy 11(2), 58 (Feb. 1996).
100. R. M. Crooks and co-workers, Spectroscopy 8(7), 28 (Sept. 1993).
101. J. P. Blitz and S. M. Augustine, Spectroscopy 9(8), 28 (Oct. 1994).
102. E. W. Thulstrup and J. Michl, Elementary Polarization Spectroscopy, VCH Publish-
ers, New York, 1989.
103. R. G. Messerschmidt and M. A. Harthcock, eds., Infrared Microspectroscopy: Theory
and Applications, Marcel Dekker, Inc., New York, 1988.
104. J. E. Katon, A. J. Sommer, and P. L. Lang, Appl. Spectrosc. Rev. 25, 173 (1989–
1990).
105. J. E. Katon and A. J. Sommer, Anal. Chem. 64, 931A (1992).
106. H. J. Humecki, ed., Practical Guide to Infrared Microspectroscopy, Marcel Dekker,
Inc., New York, 1995.
107. F. M. Mirabella, Jr., ed., Internal Reflection Spectroscopy: Theory and Applications,
Marcel Dekker, Inc., New York, 1993.
108. M. W. Urban, Attenuated Total Reflectance Spectroscopy of Polymers: Theory and
Practics, American Chemical Society, Washington, D. C., 1996.
109. R. Mendelsohn, J. W. Brauner, and A. Gericke, Ann. Rev. Phys. Chem. 46, 305
(1995).
110. J. R. Ferraro, Vibrational Spectroscopy at High External Pressures: The Diamond
Anvil Cell, Academic Press, Inc., New York, 1984.
111. R. J. H. Clark and R. E. Hester, eds., Molecular Cryospectroscopy, John Wiley &
Sons, Inc., New York, 1995; Adv. Spectrosc. 23 (1995).
112. R. J. H. Clark and R. E. Hester, eds., Time Resolved Spectroscopy, John Wiley &
Sons, Inc., New York, 1989; Adv. Spectrosc. 18 (1989).
113. M. J. Wirth, Anal. Chem. 62, 270A (1990).
114. P. F. Bernath, Ann. Rev. Phys. Chem. 41, 91 (1990).
115. U. Krull and R. S. Brown, in Ref. 35, pp. 505–532 (1998).
116. P. Klocek and G. H. Sigel, Jr., Infrared Fiber Optics, SPIE Optical Engineering
Press, Bellingham, Wash., 1989.
117. P. K. Cheo, Fiber Optics and Optoelectronics, 2nd ed., Prentice-Hall, Englewood
Cliffs, N.J., 1990.
118. R. D. Driver, G. L. Dewey, D. A. Greenberg, and J. D. Stark, Spectroscopy 9(4), 36
(May 1994).
119. A. Ganz and J. P. Coates, Spectroscopy 11(1), 32 (Jan. 1996).
120. R. Beer, in Ref. 35, pp. 85–162.
121. C. R. Webster and R. D. May, J. Geophys. Res. 92, 11931 (1987).
122. A. Rosencwaig, Photoacoustics and Photoacoustic Spectroscopy, Wiley-Interscience,
New York, 1980.
123. P. Hess and J. Pelzl, eds., Photoacoustic and Photothermal Phenomena, Springer-
Verlag, Berlin, 1987.
124. V. P. Zharov and V. S. Letokhov, Laser Optoacoustic Spectroscopy, Springer-Verlag,
Berlin, 1986.
125. J. R. Small and E. Kurian, Spectroscopy 10(9), 27 (Nov. 7–Dec. 1995).
126. P. L. Meyer and M. W. Sigrist, Rev. Sci. Instrum. 61, 1779 (1990).
127. F. J. M. Harren, J. R. Reuss, E. J. Woltering, and D. D. Bicanic, Appl. Spectrosc. 44,
1360 (1990).
128. D. J. Brassington, J. Phys. D15, 219 (1982).
129. J. R. Durig, ed., Chemical, Biological and Industrial Applications of Infrared Spec-
troscopy, John Wiley & Sons, Inc., New York, 1985.
Vol. 22 SPECTROSCOPY 23

130. J. L. Koenig, Anal. Chem. 66, 515A (1994).

131. D. Lin-Vien, N. B. Colthup, W. G. Fately, and J. G. Grasselli, The Handbook of
Infrared and Raman Characteristic Frequencies of Organic Molecules, Academic
Press, Inc., San Diego, Calif., 1991.
132. G. Socrates, Infrared Characteristic Group Frequencies, 2nd ed., John Wiley & Sons,
Inc., New York, 1994.
133. J. P. Coates, Spectroscopy 10(7), 14 (Sept. 1995).
134. R. Whites, Chromatography/Fourier Transform Infrared Spectroscopy and Its
Applications, Marcel Dekker, Inc., New York, 1990.
135. C. Fujimoto and K. Jinno, Anal. Chem. 64, 476A (1992).
136. B. W. Cook, Spectroscopy 6(6), 22 (July–Aug. 1991).
137. J. W. Washall and T. P. Wampler, Spectroscopy 6(4), 38 (May 1991).
138. T. Provder, M. W. Urban, and H. G. Barth, eds., Hyphenated Techniques in Polymer
Characterization: Thermal-Spectroscopic and Other Methods, American Chemical
Society, Washington, D.C., 1994.
139. K. S. Kalasinsky, B. Levine, M. L. Smith, and G. E. Platoff, Jr., Crit. Rev. Anal.
Chem. 23, 441 (1993).
140. I. W. Levin and E. N. Lewis, Anal. Chem. 62, 1101A–1111A (1990).
141. R. J. H. Clark and R. E. Hester, eds., Biomolecular Spectroscopy, 2 Vols., John Wiley
& Sons, Inc., New York, 1993; Adv. Spectrosc. 20 (1993).
142. H. H. Mantsch and D. Chapman, eds., Infrared Spectroscopy of Biomolecules, John
Wiley & Sons, Inc., New York, 1996.
143. W. Suëtaka, Surface Infrared and Raman Spectroscopy: Methods and Applications,
Plenum Press, New York, 1995.
144. T. B. Sauke, J. F. Becker, M. Loewenstein, T. D. Gutierrez, and C. G. Bratton, Spec-
troscopy 9(5), 34 (June 1994).
145. J. L. Koenig, Spectroscopy of Polymers, American Chemical Society, Washington,
D.C., 1992.
146. W. W. Urban and T. Provder, eds., Multidimensional Spectroscopy of Polymers:
Vibrational, NMR, and Fluorescence Techniques, American Chemical Society,
Washington, D.C., 1995.
147. K. Ashley, Talanta 38, 1209 (1991).
148. K. A. B. Lee and co-workers, Spectroscopy 8(5), 24 (June 1993).
149. H. Ahlberg, S. Lundkvist, and B. Olsson, Appl. Opt. 24, 3924 (1985).
150. D. J. Brassington, Adv. Spectrosc. 24, 85 (1995).
151. M. T. Coffey and W. G. Mankin, Spectroscopy 8(6), 22 (July–Aug. 1993).
152. M. J. Persky, Rev. Sci. Instrum. 66, 4763 (1995).
153. H. M. Heise, L. Kupper, and L. N. Butvina, Spectrochimica Acta, Part B: Atomic
Spectroscopy 57B(10), 1649 (2002).
154. J. Hurst, Chemist 79(2), 2 (2002).
155. P. Williams and K. Norris, eds., Near-Infrared Technology in the Agricultural and
Food Industries, American Association of Cereal Chemists, St. Paul, Minn., 1987.
156. J. K. Drennan, E. G. Kraemer, and R. A. Lodder, Crit. Rev. Anal. Chem. 22, 443
(1991).
157. D. A. Burns and E. W. Ciurczak, eds., Handbook of Near-Infrared Analysis, Marcel-
Dekker, Inc., New York, 1992.
158. W. F. McClure, Anal. Chem. 66, 43A (1994).
159. G. Downey, Analyst 119, 2367 (1994).
160. C. D. Tran, Anal. Chem. 64, 971A (1992).
161. J. Soos, Laser Focus World 30(8), 87 (Aug. 1994).
162. M. A. Sharaf, D. L. Illman, and B. R. Kowalski, Chemometrics, John Wiley & Sons,
Inc., New York, 1986.
24 SPECTROSCOPY Vol. 22

163. R. G. Brereton, Chemometrics: Applications of Mathematics and Statistics to

Laboratory Systems, E. Horwood, New York, 1990.
164. S. J. Haswell, ed., Practical Guide to Chemometrics, Marcel Dekker, Inc., New York,
1992.
165. J. Coates, T. Davidson, and L. McDermott, Spectroscopy 7(9), 40 (Nov.–Dec. 1992).
166. C. E. Miller, Appl. Spectrosc. Rev. 26, 277 (1991).
167. P. Castro and H. Mark, Spectroscopy 9(1), 27 (Jan. 1994).
168. E. W. Ciurczak and J. K. Drennen, Spectroscopy 7(6), 12 (July–Aug. 1992).
169. J. J. Kelly, C. H. Barlow, T. M. Jinguji, and J. B. Callis, Anal. Chem. 61, 313 (1989).
170. S. J. Swarin and C. A. Drumm, Spectroscopy 7(7), 42 (Sept. 1992).
171. J. P. Coates, Spectroscopy 9(9), 36 (Nov.–Dec. 1994).
172. J.-P. Conzen, J. Bürck, and H.-J. Ache, Appl. Spectrosc. 47, 753 (1993).
173. R. J. Dempsey, D. G. Davis, R. G. Buice, Jr., and R. A. Lodder, Appl. Spectrosc. 50(2),
18A (Feb. 1996).
174. A. Abd-Elwahed and R. Holze, Curr. Topics Electrochem. 9, 93 (2003).
175. R. F. Barrow and P. Crozet, Ann. Rep. Prog. of Chem., Sect. C: Phys. Chem. 93, 187
(1997).
176. G. Winnewisser, J. Mol. Struct. 408–409, 1 (1997).
177. P. H. Bolivar, Proc. Scottish Univ. Summer School in Phy., 151 (1999).
178. M. Choi, A. D. Bettermann, and D. W. Van Der Weide, Proc. SPIE—The Inte. Soc.
Opt. Ing. 5268, 27 (2004).
179. O. Astafiev and S. Komiyama, Electron Transport in Quantum Dots, P. Jonathan,
ed., Kluwer Academic Publishers, Norwell, Mass., 2003.
180. H. S. Chen, Space Remote Sensing Systems: An Introduction, Academic Press, Inc.,
Orlando, Fla., 1985.
181. S. V. Compton, D. A. C. Compton, and R. G. Messerschmidt, Spectroscopy 6(6), 35
(July–Aug. 1991).
182. R. C. Carlson, A. F. Hayden, and W. B. Telfair, Appl. Opt. 27, 4952 (1988).
183. A. Knowles and C. Burgess, eds., Practical Absorption Spectrometry, Chapman &
Hall, London, 1984.
184. R. C. Denney and R. Sinclair, Visible and Ultraviolet Spectroscopy, John Wiley &
Sons, Inc., New York, 1988.
185. R. Lobinski and Z. Marczenko, Crit. Rev. Anal. Chem. 23, 55 (1992).
186. H.-H. Perkampus, UV–VIS Spectroscopy and Its Applications, Springer-Verlag,
New York, 1992.
187. B. J. Clark, T. Frost, and M. A. Russell, eds., UV Spectroscopy: Techniques, Instru-
mentation, Data Handling, Chapman & Hall, London, 1993.
188. I. R. Altemose, J. Chem. Educ. 63, A216, A262 (1986).
189. J. A. R. Sampson, Techniques of Vacuum Ultraviolet Spectroscopy, John Wiley &
Sons, Inc., New York, 1967.
190. A. N. Zaidel’ and E. Ya Shreider, Vacuum Ultraviolet Spectroscopy, Humphrey
Science Publishers, Ann Arbor, Mich., 1970.
191. G. Stark and P. L. Smith, in Ref. 90, pp. 487–498.
192. J. V. Sweedler, R. D. Jalkian, and M. B. Denton, Appl. Spectrosc. 43, 953 (1989).
193. R. E. Fields and co-workers, Spectroscopy 7(9), 28 (Nov.–Dec. 1992).
194. J. P. Kotthaus, Science 286(5448), 2287 (1999).
195. E. M. Westbrook and I. Naday, Methods Enzymol. 276, 244 (1997).
196. Y.-C. Lo, Proc. of SPIE—The Int. Soc. Opt. Eng. 3422, 70 (1998).
197. R. A. Yotter and D. M. Wilson, IEEE Sensors J. 3(3), 288 (2003).
198. R. Williams, Appl. Spectrosc. Rev. 25, 63 (1989).
199. J. T. Brownrigg, Proc. Control Quality 2(1), 1 (1992).
200. G. Talsky, Derivative Spectrophotometry, VCH Publishers, New York, 1994.
Vol. 22 SPECTROSCOPY 25

201. C. B. Ojeda, F. S. Rojas, and J. M. C. Pavon, Talanta 42, 1195 (1995).

202. The Sadtler Handbook of Ultraviolet Spectra, Sadtler Research Laboratories, Phila-
delphia, Pa., 1979, and updates.
203. R. M. Silverstein, G. C. Bassler, and T. C. Morrill, Spectrometric Identification of
Organic Compounds, 5th ed., John Wiley & Sons, New York, 1991.
204. H.-H. Perkampus, UV–VIS Atlas of Organic Compounds, 2nd ed., VCH Publishers,
New York, 1992.
205. I. Sunshine, CRC Handbook of Spectrophotometric Data of Drugs, CRC Press, Boca
Raton, Fla., 1981.
206. S. Görög, Ultraviolet—Visible Spectrophotometry in Pharmaceutical Analysis, CRC
Press, Boca Raton, Fla., 1995.
207. E. Sevick-Muraca and D. Benaron, eds., Biomedical Optical Spectroscopy and Diag-
nostics, Optical Society of America, Washington, D.C., 1996.
208. W. R. LaCourse and C. O. Dasenbrock, Anal. Chem. 10(12), 37R (1998).
209. G. G. Andersson, B. K. Dable, and K. S. Booksh, Chemomet Intell. Lab. Systems
49(2), 195 (1999).
210. H.-L. Shen, B. Grung, O. M. Kvalheim, and I. Eide, Ana. Chim. Acta 446(1–2), 313
(2001).
211. S. Posello, Laboratorio 2000 15(5), 34 (2001).
212. M. Wasim, M. S. Hassan, and R. G. Brereton, Analyt 128(8), 1082 (2003).
213. R. E. Huffman, Atmospheric Ultraviolet Remote Sensing, Academic Press, Inc.,
Boston, Mass., 1992.
214. J. M. C. Plane and N. Smith, Adv. Spectrosc. 24, 223 (1995).
215. B. J. Clark, T. Frost, and M. A. Russel, eds., UV Spectroscopy—Techniques, Instru-
mentation, Data Handling, Chapman & Hall, 1993.
216. W. Schmidt, Optical Spectroscopy in Chemistry and Life Sciences, Wiley-VCH, Wein-
heim, 2005.
217. G. Svehla, ed., Analytical Visible and Ultraviolet Spectrometry in Comprehensive
Analytical Chemistry, Vol. XIX, Elsevier, Amsterdam, The Netherlands, 1986.
218. D. Lübbers and N. Opitz, Z. Naturf. 30c, 532 (1975).
219. G. Gauglitz, in H. Baltes, W. Göpel, and J. Hesse, eds., Sensors Update, Vol. I, VCH
Verlagsgesellschaft, Weinheim, 1996.
220. G. Gauglitz, Anal. Bioanal. Chem. 381(1), 141 (2005).
221. G. Gauglitz, Rev. Sci. Instr. 76(6), 062224/1 (2005).

GÜNTER GAUGLITZ
Universität Tübingen
26 SPECTROSCOPY Vol. 22

Table 1. Regions of the Electromagnetic Spectrum

Wavelength Frequency or Transitions observed or
Region limitsa photon energya excited
radio waves > 30 cm < 1,000 MHz hyperfine structure from
nuclear spins and isotopic
shifts
microwaves 1 mm–30 cm 300–1 GHz rotation and inversion of
molecules; cyclotron
resonance of electrons
in solids
far-infrared (fir) 50–1000 mm 200–10 cm
1 molecular rotations and
(sub-millimeter certain low frequency
waves) bending, torsional, and
skeletal vibrations;
lattice modes in solids
mid-infrared 2.5–50 mm 4,000–200 cm
1 fundamental molecular
vibrations (rovibrational
spectra)
near-infrared (nir) 0.8–2.5 mm 12,500–4,000 cm
1 vibrational overtones and
combinations
visible (vis)b 400–800 nm valence electrons
(0.4–0.8 mm)
near-ultraviolet 200–400 nm valence electrons (atomic
(uv)c and rovibronic molecular
spectra)
vacuum ultraviolet 10–200 nm 125–6 eV inner-shell electrons;
(vuv) ionization
X-rays 0.01–10 nm 125–0.125 keV inner-shell electrons;
(0.1–100) nuclear
g-rays <0.01 nm >0.125 MeV nuclear
a
Values are approximate.
b
Also defined as 380–780 nm by DIN-NORM 5031.
c
Also defined as 200–380 nm by DIN-NORM 5031.
Vol. 22 SPECTROSCOPY 27

Table 2. Line-Shape Parameters

Transitions
Valence
Parameter Rotational Vibrational electronic
n, cm
1
line frequency, ˜e 1–100 100–4,000 <50,000(>200 nm)
natural linewidth,
n eN , cm
1 <10
11 <10
7 <3  10
3
Doppler width at 300 K,
n eD , cm
1 <0.0005 <0.01 0.01–0.2 (0.0005 nm)
natural radiative lifetime, tN, s >10
1 >2  10
4 >2  10
9
peak Doppler-broadened absorption <10
20 10
18 10
11 –10
16a <10
17b
cross-section, sA, cm2
peak differential scattering cross
section, d s/d W, cm2/sr
Rayleigh negligible negligible <2  10
13a,c <10
26b,d
Raman <10
27 <10
28 10
24a
<5  10
16a,e
fluorescence negligible negligible 10
20 –10
25b
a
Values are for atoms.
b
Values are for molecules.
c
Values are for resonant scattering by atomic vapors.
d
Values are for nonresonant scattering of visible and near-uv radiation by atmospheric gases; reso-
nant Raman scattering approaches 10
24 cm2/sr.
e
Values are for STP atmospheric conditions.
28 SPECTROSCOPY Vol. 22

Table 3. Components and Materials Used in uv–vis–ir Spectroscopya

Instrumental Near-uv, visible, and
parameter Far-infraredb Mid-infraredc near-ird
broad-band plasma emission blackbodies: Nernst deuterium lamp (160–370 nm)
thermal from high glower (zirconia), Xe arc lamp (300 nm–1.3 mm)
sources pressure globar (silicon quartz-envelope tungsten–
mercury arc carbide), halogen lamp
lamp nichrome (350 nm–2.5 mm)
wire cole
continuously CO2 laser OPO (16 mm) organic dye lasers (320 nm–
tunable frequency color-center 1.3 mm) OPO (>410 nm)
laser difference lasers (1.5–4 mm) Ti:sapphire laser (700–1000
sources generation nonlinear optical nm) frequency conversion of
(65–1000 mm) mixing (2–9 mm) other lasers (>190 nm) diode
microwave semiconductor lasers (>670 nm)
sideband mixing diodes (3–28 mm)
(> 70 mm) spinflip Raman
(5–6 mm)
waveguide
CO2 (9–11 mm)
detectors pyroelectric photoconductors photomultipliers (120 nm–
(DTGS, LT) (<40 mm) 1.1 mm) photodiodes
doped-germanium (InSb; doped (InAs, InGaA, Si, Ge)
and InSb germanium; photoconductors (Si, Ge)
bolometers MCT) thermal
Golay pneumatic (thermocouples,
cell bolometers)
pyroelectric
(DTGS, LT)
array none PtSi (<5 mm) InSb silicon arrays (175 nm–1.1 mm)
detectors (<5 mm) MCT photographic emulsions
(<12 mm) doped (<1.2 mm) Ge arrays
Si (10–30 mm) (700 nm–1.5 mm)
InSb, PbSe, PtSi
general polyethylene, alkali halide alkali halide crystals
optical Mylar quartz crystals glass (300 nm–2.2 mm)
materials diamond fluorite, CaF2 quartz (170 nm–3.5 mm)
(>6 mm) (<9 mm) ZnSe diamond (220 nm–4 mm)
(800 nm–20 mm) sapphire (150 nm–6 mm)
AgCl (420 nm– fluorite (120 nm–9 mm)
25 mm) KRS-5
(550 nm–40 mm)
fiber optics none fluoride glasses silica glasses quartz
(900 nm–5 mm) (250 nm–1.3 mm)
chalcogenide
glasses (2.2–
12 mm) hollow
metal fibers
(10 mm)
a
DTGS ¼ deuterated triglycine sulfate; KRS-5 ¼ mixed thallium bromide–iodide; LT ¼ lithium tanta-
late; MCT ¼ mercury cadmium telluride; and OPO ¼ optical parametric oscillator.
b
50–1000 mm.
c
2.5–50 mm.
d
200 nm–2.5 mm.
Vol. 22 SPECTROSCOPY 29

Fig. 1. Arrangements for absorption, fluorescence, and reflection measurements.

E -field l

Incident
k = (hν/c)z Transmitted light
light, I0

Induced dipole

Scattered light

R
(a)

∆ν
I0
Is ∆ν
It
ν0 ν0

(b) (c)

Fig. 2. An incident electromagnetic field of intensity, I0, having an associated electric

field, E, induces dipole oscillation in the absorbers. The transmitted intensity, It, is re-
duced by absorption; of the radiated (scattered) light, a portion, Is, is shown here detected
in a conventional right-angle configuration with collection solid angle D0. (a) Schematic
of the absorption/scattering, where I0 ¼ ð12Þ ce0 j E j2 in W/m2; (b) plot of scattered light,
Is, versus frequency, where Is ¼ I0 Nlðds=dÞ 
c , and Dc is proportional to (detector
area)/R2; and (c) plot of transmitted light, It, versus frequency, where It ¼ I0 exp ð
Ns1Þ
 I0 ð1
NslÞ for Nsl 1.
30 SPECTROSCOPY Vol. 22

Fig. 3. Principle set-ups for absorbance, scattering, and emission measurements is depen-
dant on the wavenumber region. Independent of the wavenumber in optical spectroscopy
instrumentation contains source, frequency selection (element of dispersion: monochro-
mator), sample compartment and detection unit. Absorbance is measured along the optical
axis, scattering and luminescence in the perpendicular axis. In uv–vis spectroscopy, the
monochromator is placed in front of the sample (photodegradation) and in ir behind the
sample (self-radiation of sample) (see also Refs. 45,46.)