654CHAPTER 24

Introduction to Spectrochemical Methods

24B Interaction of Radiation and Matter

The most interesting and useful interactions in spectroscopy are those in which tran-
sitions occur between different energy levels of chemical species. Other interactions,
such as reflection, refraction, elastic scattering, interference, and diffraction, are often
related to the bulk properties of materials rather than to the unique energy levels of
specific molecules or atoms. Although these bulk interactions are also of interest in
Table 24-2
spectroscopy, we will limit our discussion here to those interactions in which energy
Regions of the UV, Visible, and level transitions occur. The specific types of interactions observed depend strongly on
IR Spectrum
the energy of the radiation used and the mode of detection.
Region Wavelength Range
UV 180380 nm
Visible 380780 nm 24B-1The Electromagnetic Spectrum
Near-IR 0.782.5 m
Mid-IR 2.550 m The electromagnetic spectrum covers an enormous range of energies (frequencies)
and thus wavelengths (see Table 24-2). Useful frequencies vary from .1019 Hz
(g-ray) to 103 Hz (radio waves). An X-ray photon (n < 3 3 1018 Hz, l < 10210 m),
One easy way to recall the order
of the colors in the spectrum is for example, is 10,000 times as energetic as a photon emitted by an ordinary light
bulb (n < 3 3 10 14 Hz, l < 10 26 m) and 10 15 times as energetic as a radio-
by the mnemonic ROY G BIV,
which is short for Red, Orange, frequency photon (n < 3 3 103 Hz l < 105 m).
Yellow, Green, Blue, Indigo, and The major divisions of the spectrum are shown in color in Color Plate 21. Note
Violet. that the visible region, to which our eyes respond, is only a tiny fraction of the entire
spectrum. Different types of radiation such as gamma (g) rays or radio waves differ
from visible light only in the energy (frequency) of their photons.
The visible region of the spectrum Figure 24-3 shows the regions of electromagnetic spectrum that are used for
extends from about 400 nm to almost spectroscopic analyses. Also shown are the types of atomic and molecular transi-
800 nm (see Table 24-2). tions that result from interactions of the radiation with a sample. Note that the

Change of
Type of Change of Change of nuclear
quantum change: Change of spin orientation configuration Change of electron distribution configuration

or

Wavenumber, cm21
1022 1 100 104 106 108

Wavelength
10 m 100 cm 1 cm 100 mm 1000 nm 10 nm 100 pm

Frequency, Hz
3 3 106 3 3 108 3 3 1010 3 3 1012 3 3 1014 3 3 1016 3 3 1018

Energy, J/mol
1023 1021 10 103 105 107 109

Type of NMR ESR Microwave Infrared Visible and X-ray -ray

spectroscopy: ultraviolet

Figure 24-3The regions of the electromagnetic spectrum. Interaction of an analyte with electromagnetic radiation can result
in the types of changes shown. Note that changes in electron distributions occur in the UV/visible region. The wavenumber,
wavelength, frequency, and energy are characteristics that describe electromagnetic radiation. (From C. N. Banwell, Fundamentals
of Molecular Spectroscopy, 3rd ed., New York; McGraw-Hill, 1983, p. 7.)

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 24BInteraction of Radiation and Matter655

low-energy radiation used in nuclear magnetic resonance (NMR) and electron spin
resonance (ESR) spectroscopy causes subtle changes, such as changes in spin; the
high-energy radiation used in g-ray spectroscopy can cause much more dramatic
changes, such as nuclear configuration changes.
Spectrochemical methods that use not only visible but also ultraviolet and infrared
radiation are often called optical methods in spite of the fact that the human eye is Optical methods are spectroscopic
not sensitive to UV or IR radiation. This terminology arises from the many common methods based on ultraviolet, visible,
features of instruments for the three spectral regions and the similarities in the way we and infrared radiation.
view the interactions of the three types of radiation with matter.

24B-2Spectroscopic Measurements
Spectroscopists use the interactions of radiation with matter to obtain information
about a sample. Several of the chemical elements were discovered by spectroscopy
(see Feature 24-1). The sample is usually stimulated in some way by applying en-
ergy in the form of heat, electrical energy, light, particles, or a chemical reaction.
Prior to applying the stimulus, the analyte is predominately in its lowest-energy or
ground state. The stimulus then causes some of the analyte species to undergo a
transition to a higher-energy or excited state. We acquire information about the
analyte by measuring the electromagnetic radiation emitted as it returns to the
ground state or by measuring the amount of electromagnetic radiation absorbed A familiar example of chemilumines-
as a result of excitation. cence is found in the light emitted by
a firefly. In the firefly reaction, an en-
Figure 24-4 illustrates the processes that occur in emission and chemilumines- zyme luciferase catalyzes the oxidative
cence spectroscopy. The analyte is stimulated by applying heat or electrical energy or phosphorylation reaction of luciferin
by a chemical reaction. The term emission spectroscopy usually refers to methods with adenosine triphosphate (ATP) to
in which the stimulus is heat or electrical energy, while chemiluminescence spec- produce oxyluciferin, carbon dioxide,
troscopy refers to excitation of the analyte by a chemical reaction. In both cases, adenosine monophosphate (AMP),
and light. Chemiluminescence involv-
measurement of the radiant power emitted as the analyte returns to the ground state
ing a biological or enzyme reaction is
can give information about its identity and concentration. The results of such a mea- often termed bioluminescence. The
surement are often expressed graphically by a spectrum, which is a plot of the emitted popular light stick is another familiar
radiation as a function of frequency or wavelength. example of chemiluminescence.

Emitted 2
radiation E21 5 h 21 5 hc/ 21
PE 1
Figure 24-4Emission or chemilumi-
E2 5 h 2 5 hc/ 2 nescence processes. In (a), the sample
E1 5 h 1 5 hc/ 1 is excited by applying thermal, electrical,
Sample 0 or chemical energy. No radiant energy
(b) is used to produce excited states, and so,
these are called non-radiative pro-
cesses. In the energy level diagram (b),
PE
the dashed lines with upward pointing
arrows symbolize these nonradiative
excitation processes, while the solid
lines with downward pointing arrows
indicate that the analyte loses its energy
by emission of a photon. In (c), the re-
Thermal, electrical,
sulting spectrum is shown as a measure-
or chemical energy 2 1 21
ment of the radiant power emitted, PE,
(a) (c) as a function of wavelength, l.

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deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.