Ch.

6: Introduction to Spectroscopic methods

Spectroscopy:
A branch of science that studies the interaction
between EM radiation and matter.
Spectrometry and Spectrometric methods :
Measurement of the intensity of radiation with a
photoelectric transducer or other types of electronic
device.

1
 What is Electromagnetic Radiation?

• EMR is a form of energy that has both Wave and

Particle Properties.
• Many of the properties of electromagnetic radiation are
conveniently described by means of a classical
sinusoidal wave model, which embodies such
parameters as wavelength, frequency, velocity, and
amplitude.
• In contrast to other wave phenomena, such as sound,
electromagnetic radiation requires no supporting
medium for its transmission and thus passes readily a
vacuum.

2
 EMR as a Wave
For many purposes, electromagnetic radiation is conveniently
represented as electric and magnetic field that undergo in-phase,
sinusoidal oscillations at right angles to each other and to the direction
of propagation.

Figure-6.1(a) Representation of a single ray of plane-polarized electromagnetic

radiation. The term plane polarized implies that all oscillations of either the
electric or the magnetic fields lie within a single plane.
3
Figure -6.1(b) is a two –dimensional representation of the electric vector
component of the ray in 6(a).

4
 Properties of electromagnetic radiation

 Period (p) – the time

required for one cycle to
pass a fixed point in space.

 Frequency (V) – the number

of cycles which pass a fixed
point in space per second.
=1/p

 Amplitude (A) – The maximum length of the electric vector in the

wave (Maximum height of a wave).

 Wavelength () – The distance between two identical adjacent

points in a wave (usually maxima or minima).

 Wavenumber (1/) - The number of waves per cm in units of cm-1.

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 5

 Velocity of propagation = vi = n . i
Speed of light = Frequency x Wavelength
 Frequency of a beam of radiation is determined by the source and
invariant
 Velocity of radiation depends upon the composition of the medium
through which it passes.

For electromagnetic waves the Speed (c) in vacuum is a Constant

Speed of light in vacuum = c = 2.99792x108 m/s = c = n . 
Speed of light in air = only 0.03% less than the one in vacuum.
Therefore for either air or vacuum; c = 3.00 x 108 m/s

In any medium containing matter, propagation of radiation is slowed

by the interaction between the electromagnetic field of the radiation
and the bound electrons in the matter. Since the radiant frequency is
invariant and fixed by the source, the wavelength must decrease as
radiation passes from a vacuum to another medium.
 Effect of the Medium on a Light Wave

• Frequency remains the same.

• Velocity and Wavelength change.

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 7

 This constant speed means a direct, Inverse Relationship
Between Wavelength and Frequency

n ∝ 1/ 
The relationship between frequency n of light and energy E,

Planck’s Equation: E = hn ;
Where h = Planck’s constant
= 6.6 x 10-27 erg.sec = 6.6 x 10-34 joule.sec

In vacuum, velocity of light → c = n = 3 x 1010 cm/s which gives,

n = c/
E = h(c/) = hcv (where, v = 1/ = wavenumber)

Energy directly proportional to wavenumber

8
 The Electromagnetic Spectrum

 The Higher the Frequency the Shorter the Wavelength

 The Longer the Wavelength, Lower the Frequency.

9
10
 Mathematical Description of a Wave

Sine waves with different amplitudes and with a phase different of 90 degree

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 11

 Mathematical Description of a Wave
A wave can be described by an equation for a sine wave
Y = A sin(wt + f)
Y= magnitude of the
electric field at time t,
A = Amplitude
f = phase angle
w= angular velocity
w = 2pn = 2pv

The angular velocity is
related to the frequency
of the radiation

Y = A sin(2pnt + f)
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 12
 Superposition of Waves
 If two plane-polarized waves overlap in space, the
resulting electromagnetic disturbance is the algebraic
sum of the two waves.
Y = A1sin(2pn1t + f1) + A2sin(2pn2t + f2) +…….

Superposition of sinusoidal wave: (a) A1 < A2, (1 - 2) = 20º, n1 = n2;
13
(b) A1 < A2, (1 - 2) = 200º, n1 = n2
 Optical Interference
Optical Interference: The interaction of two or more light waves
yielding an irradiance that is not equal to the sum of the irradiances.

-Constructive Interference
1) Have identical frequency
2) f2 – f1 = d = m2p
f2 – f1 = 0, or 360 deg or
integer multiple of 360 deg.

- Destructive Interference
1) Have identical frequency
2) f2 – f1 = d = (2m+1)p
f2 – f1 = 180 deg or 180 +
integer multiple of 360 deg.

Figure 3-4 – Ingle and Crouch, 14

Periodicity or Beat
Superposition of two sinusoidal wave of different frequencies but identical amplitudes.
 The resultant wave is no longer sinusoidal but exhibit a periodicity
 (a) wave1 period= 1/n1,
(b) wave2 period= 1/n2 n2 = 1.25 n1; (c) combined wave pattern result: 1/ n
n= n1 - n2 

Should be n

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 15

An important aspect of superposition is that:
 a complex waveform can be broken down into simple components
by a mathematical operation called the Fourier transformation.
 Jean Fourier (1768-1830) demonstrated that, any periodic
function, regardless of complexicity , can be described by a sum
of simple sine or cosine terms.
 of the original signal. The Fourier transform decomposes
a function of time (a signal) into the frequencies that make it up.
The Fourier transform is called the frequency domain
representation
FT is a tedious and time consuming when done by hand.
Efficient computer programs are necessary.

16
Diffraction:
The Bending of Light as It Passes Through an Aperture
or Around a Small Object
Diffraction is a consequence
of interference
 not only observed for EMR
but also for mechanical or
acoustical waves
- For example, diffraction is easily
demonstrated in the laboratory by
mechanically generating waves of
constant frequency in a tank of
water and observing the wave
crests before and after they pass
through a rectangular opening, or
slit

17
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007
Diffraction of Waves in a Liquid
 Diffraction increases as aperture size  

 When the slit is wide relative to the wavelength (a),

diffraction is slight and difficult to detect.
 when the wavelength and the slit opening are of the
same order of magnitude diffraction becomes more
pronounced. Here, the slit behaves as a new source
from which waves radiate in a series of nearly
180arcs. The direction of the wave front appears to
bend as a consequence of passing the two edges of
the slit

18
Eugene Hecht, Optics, Addison-Wesley, Reading, MA, 1998.
 Diffraction Pattern From Multiple Slits
- If the radiation is monochromatic, a series of dark and light images is
observed.

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 19

 Diffraction Pattern From Multiple Slits

If slit width → 
The band intensities
decrease only
gradually with
increasing distances
from the central band.
If slit width >
The decrease is much
more pronounced

https://app.jove.com/science-education/v/11296/interference-and-diffraction-wave-
nature-of-light

https://app.jove.com/v/10424/interference-diffraction-single-and-double-slit-experiments

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 20

 Diffraction Pattern From Multiple Slits
The conditions for maximum
constructive interference can be
derived. =diffraction angle
BD and CD are the light paths from
the slits B and C to the point D.
Assumption: OE >>> BC
then, BD  OD  CD
BF CD and forms BCF triangle
And BCF  DOE
Angle CBF = =diffraction angle

CF = BC sin  = n
Example 6.1. OE= 2.0 m, BC= 0.3 mm, n=4
=? İf DE=15.4 mm DE= OD sin   Sin = DE/OD
0.3 mm x 15.4 mm = 4 x 
2.0 m x 1000 mm/m BC. DE = n
OD=OE
 = 5.78 x 10-4 mm 578 nm
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 21
 Coherent Radiation
Coherency: When two waves have an initial phase difference of zero
or constant for a long time, they are considered coherent.


Conditions for coherency of two sources of radiation are:

1. They must have identical frequencies and

2. The phase relationships between the two remains constant with

time

Incoherency test: Illuminate the slits with W-lamp-

result is ;
- disappearance of the dark and light patterns
- more or less uniform illumination of the screen

This behaviour is the consequence of the incoherent character of

W-lamp.

22
 Incoherent sources
Light is emitted by individual atoms or molecules
 resulting beam is the summation of countless individual events
 phase differences are variable
 constructive and destructive interferences occur randomly
 average of the emissions are observed as an illumination

Coherent sourses
 optical lasers, rf oscilators, microwave sources.

23
6B-7 Transmission of Radiation: The Refractive Index
Experimental observations show that
the rate radiation propagates through
a transparent substance is less than
its velocity in a vacuum and depends
on the kinds and concentrations of
atoms, ions, or molecules in the
medium
 Each medium has a characteristic
“index of refraction” that is defined as
the ratio between the speed of light in
vacuum and the speed of light in the
c
medium.

 Light travels more slowly in a v i

medium with a high index of refraction

c is the speed of light in vacuum in (m/s),
and more quickly in a medium with a v is the speed of light in the medium in (m/s).
low index of refraction.

24
 The refractive index of most
liquids lies between 1.3 and 1.8
 it is 1.3 to 2.5 or higher for solids.

25
 Dispersion and Prisms
• Since the velocity of radiation in matter is wavelength dependent and since c
in Equation 6-11 is independent of wavelength, the refractive index of a
substance must also change with wavelength
• The variation in refractive index of a substance with wavelength or
frequency is called Dispersion
c

vi
Normal Dispersion:
A region where gradual increase
in ŋ wrt increase in frequency.

Anomalous Dispersion:
Frequency ranges in which a
sharp change in ŋ is observed.

Dispersion curves are imp. when choosing materials for the optical components
of spectrometer. ND( lenses) AD(prisms) 26
 6B-8 Refraction of Radiation
- Refraction is the change in direction of propogation of a wave due
to a change in its transmission medium.
- Refraction of light in passing from less dense to a more dense
medium, bending is towards the normal.
- If the beam passes from more dense to a less dense medium,
bending away from the normal occurs

- The extent of refraction is given by ,

Snell’s Law: n1sin1 = n2sin2 v2sin1 = v1sin2
27
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007
Refraction:
An object (in this case a pencil)
partially immersed in water looks
bent due to refraction

28
Another example of refraction is the dispersion of white light into its
individual colors by a glass prism. As visible light exits the prism, it is
refracted and separated into a magnificent display of colors.

29
6B-9 Reflection of Radiation
Reflection is the change in direction of a wavefront at an interface
between two different media so that the wavefront returns into the
medium from which it originated.

For monochromatic light hitting

a flat surface at 900

I r (n 2  n1 ) 2
 2 1 2
I 0 (n  n )
I0: intensity of incident light
Ir: reflected intensity

Laws of reflection:
1. The incident ray, the reflected ray and the normal to the
reflection surface at the point of the incidence lie in the same
plane.
2. The reflected ray and the incident ray are on the opposite
sides of the normal. 30
Reflection of Radiation
Specular reflection: Reflection of Diffuse reflection: Reflection of light
light from a smooth surface (mirror from a rough surface. (retaining the
like) energy but losing the image)

Reflections on still water are an

example of specular reflection

31
r() at different interfaces
Reflectance is the fraction of the incident radiant energy reflected.

Ingle and Crouch, Spectrochemical Analysis 32

6B-10 Scattering of Radiation
The fraction of radiation transmitted at all angles from its
original path
 Rayleigh scattering : Molecules or aggregates of molecules with
dimensions significantly smaller than  of radiation. Intensity is
proportional to the inverse fourth power of the wavelength. I  1/4
• Blue color of the sky.
 Scattering by big molecules (Tyndall effect):
Colloidal dimensions particles, scattering can be seen by naked eye.

 used for measuring particle size and shapes of polymer molecules

 Raman Scattering:

Involves quantized frequency changes. These changes are the

results of vibrational energy level transitions that occur in the
molecule as a consequence of the polarization process.
 6B-11 Polarization of Radiation
• The interaction involved in transmission can be ascribed to periodic polarization of the
atomic and molecular species that make up the medium.
• Polarization in this context means the temporary deformation of the electron clouds
associated with atoms or molecules that is brought about by the alternating
electromagnetic field of the radiation.
• Provided that the radiation is not absorbed, the energy required for polarization is
only momentarily retained (10-14 to 10-15 s) by the species and is reemitted without
alteration as the substance returns to its original state.
• Since there is no net energy
change in this process, the
frequency of the emitted
radiation is unchanged, but
the rate of its propagation is
slowed by the time that is
required for retention and
reemission to occur.
• Thus, transmission through
a medium can be viewed
as a stepwise process that
involves polarized atoms,
ions, or molecules as
intermediates
34
•Figure 6-12a shows a few of the vectors depicted in Figure 6-11b at the instant the wave
is at its maximum. The vector in anyone plane, say XY as depicted in Figure 6-12a. can
be resolved into two mutually perpendicular components A B and CD as shown in Figure
6-12b.
•If the two components for all of the planes shown in Figure 6-12a are combined, the
resultant has the appearance shown in Figure 6-12c. Removal of one of the two resultant
planes of vibration in Figure 6-12c produces a beam that is plane polarized.

The resultant electric

vector of a plane-
polarized beam then
occupies a single
plane. Figure 6-11c
shows an end-on view
of a beam of plane-
polarized radiation
after various time
intervals.

35
 Polarizers: a Nicol prism- Birefringent polarizer
that consists of a crystal of calcite
the wire-grid polarizer which has been split and rejoined with
Canada balsam. The crystal is cut
such that the o- and e-rays are in
orthogonal linear polarization states

- the wire-grid polarizer, which consists of a

regular array of fine parallel metallic wires,
placed in a plane perpendicular to the
incident beam. Electromagnetic waves A Wollaston prism is another birefringent
which have a component of their electric polarizer consisting of two triangular
fields aligned parallel to the wires induce calcite prisms with orthogonal crystal axes
the movement of electrons along the length that are cemented together. At the internal
of the wires. Since the electrons are free to interface, an unpolarized beam splits into
move in this direction, the polarizer two linearly polarized rays which leave the
behaves in a similar manner to the surface prism at a divergence angle of 15°–45°.
of a metal when reflecting light, and the
wave is reflected backwards along the
incident beam (minus a small amount of
energy lost to joule heating of the wire).[5

36
 6C-Quantum-Mechanical Properties of EMR
6C-1 The Photoelectric Effect

-The photoelectrons are attracted

to the anode when it is positive
with respect to the cathode.
- When the anode is negative as
shown, the electrons are
“stopped”, and no current
passes.
- The negative voltage between
the anode and the cathode when
the current is zero is the stopping
potential.
FIGURE 6-13
Apparatus for studying the photoelectric effect.
Photons enter the phototube, strike the cathode,
and eject electrons.

Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007 37

 •Current is proportional to the intensity of the
radiation
•V0 depends on the frequency of the
radiation and the chemical composition of
the coating on the photocathode
•V0 independent of the intensity of the
Cut-off n incident radiation

KEm = hν – ω
h: Planck’s constant = 6.62x10-34 J.sec.
ω: work function
: energy required to remove an e- from
the surface

E = hν = KEm + ω
FIGURE 6-14 Maximum kinetic energy of
photoelectrons emitted from three metal The photoelectric effect cannot be
surfaces as a function of radiation explained by a classical wave model but
frequency. The y-intercepts (-ω) are the requires instead a quantum model, in
work functions for each metal. If incident
which radiation is viewed as a stream of
photons do not have energies of at least hv
= ω, no photoelectrons are emitted from the discrete bundles of energy, or photons a
photocathode.
38
Douglas A. Skoog, et al. Principles of Instrumental Analysis, Thomson, 2007
Energy States of Chemical Species
• Quantum theory by Planck (1900)
• Black body radiation
• Atoms, ions, and molecules exist in discrete states
• Characterized by definite amounts of energy
• When changes of state involve, the absorption or emission of
energy occur

• E1-E0 = hn = hc/

where :
E1 is the energy of the higher state and
E0 the energy of the lower state.
c : the speed of light and
h: the Planck constant,
respectively.

39
Interaction of Radiation and Matter:
Emission and Chemiluminescence Process

In the energy level diagram (b), the dashed lines with upward-
pointing arrows symbolize these non-radiative 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 resulting

In (a), the sample is spectrum is shown as a
excited by the measurement of the
application of radiant power emitted
thermal, electrical, PE as a function of
or chemical energy. wavelength, λ.

40
Interaction of Radiation and Matter
Absorption Process:
When some of the incident radiation is
absorbed, it promotes some of the analyte
species to an excited state. In absorption
spectroscopy, we measure the amount of light
absorbed as a function of wavelength. This
can give both qualitative and quantitative
information about the sample.

FIGURE 6-16- Absorption methods. Radiation of incident radiant power P0 can be

absorbed by the analyte, resulting in a transmitted beam of lower radiant power P. For
absorption to occur, the energy of the incident beam must correspond to one of the
energy differences shown in (b). The resulting absorption spectrum is shown in (c).
41
Interaction of Radiation and Matter
Photoluminescence method (Fluorescence and phosphorescence)
In photoluminescence spectroscopy the emission of photons is measured after absorption. The most
important forms of photoluminescence for analytical purposes are fluorescence and phosphorescence
spectroscopy.

FIGURE 6-17(a) Photoluminescence methods

(a) Fluorescence and phosphorescence result from
absorption of electromagnetic radiation and then
dissipation of the energy emission of radiation

In (b). the absorption can cause excitation of the

analyte to state 1 or state 2. Once excited, the
excess energy can be lost by emission of a photon
(luminescence, shown as solid line) or by
nonradiative processes (dashed lines).

(c) The emission occurs over all angles, and the wavelengths emitted correspond to energy
differences between levels. The major distinction between fluorescence and phosphorescence is the
time scale of emission, with fluorescence being prompt and phosphorescence being delayed.
42
Interaction of Radiation and Matter
Inelastic Scattering in Raman Spectroscopy
When radiation is scattered, the interaction of the incoming radiation with the sample may be elastic
or inelastic. In elastic scattering, the wavelength of the scattered radiation is the same as that of the
source radiation. The intensity of the elastically scattered radiation is used to make measurements in
nephelometry and turbidimetry, and particle sizing.

Raman spectroscopy, which is mentioned briefly in Section

6B-10 and is discussed in detail in Chapter 18, uses
inelastic scattering to produce a vibrational spectrum of
sample molecules. In this type of spectroscopic analysis, the
intensity of the scattered radiation is recorded as a function
of the frequency shift of the incident radiation. The intensity
of Raman peaks is related to the concentration of the
analyte.

43
Emission of Radiation:
Electromagnetic radiation is produced when excited Emission
particles (atoms, ions, or molecules) relax to lower energy
 X*  X + hn
levels by giving up their excess energy as photons.

Excitation needs energy!

•bombardment with electrons or other elementary particles, which generally leads to the
emission of X-radiation;
•exposure to an electric current, an AC spark, or an intense heat source (flame, DC arc, or
furnace), producing ultraviolet, visible, or infrared radiation;
•irradiation with a beam of electromagnetic radiation, which produces fluorescence radiation;
and
•an exothermic chemical reaction that produces chemiluminescence

44
Emission: Saltwater in a flame

45
 Line Spectra
- Arises from individual, well separated atoms in a gas phase
- Sharp lines (10-4 A)
E0 : the lowest, or ground-state energy of the atom.
E1 and E2 : two higher-energy electronic levels

• the single outer electron in the GS for a sodium

atom is located in the 3s orbital.
• when this electron has been promoted to the 3p
state by absorption of thermal, electrical, or
radiant energy.
• After perhaps 10-8 s, the atom returns to the
ground state, emitting a photon whose frequency
and wavelength are given by

• The line at about 590 nm is the result of the 3p

to 3s transition.
• For the sodium atom, corresponds to the more
energetic 4p state; the resulting emitted radiation
2 appears at a shorter wavelength or a higher
frequency. The line at about 330 nm results from
this transition.
46
 Band Spectra - an electron excited to one of the higher
- Arises from small molecules and radicals vibrational levels of an electronic state relaxes to
- consist of a series of closely spaced lines the lowest vibrational level of that state before an
that are not fully resolved by the instrument electronic transition to the ground state can occur.
- numerous quantized vibrational levels that - Therefore, the radiation produced by the electrical
are superimposed on the ground-state or thermal excitation of polyatomic species nearly
electronic energy level of a molecule are always results from a transition from the lowest
involved vibrational level of an excited electronic state to
any of the several vibrational levels of the ground
state
- The mechanism by which a vibrationally excited
species relaxes to the nearest electronic state
involves a transfer of its excess energy to other
atoms in the system through a series of collisions.
This process takes place at an enormous speed.
Relaxation from one electronic state to another
can also occur by collisional transfer of energy,
but the rate of this process is slow enough that
relaxation by photon release is favored.
- For a real molecule, the number of individual lines
is much larger because in addition to the
Vibrational levels numerous vibrational states, a multitude of
rotational states are superimposed on each.
- The differences in energy among the rotational
levels are perhaps an order of magnitude smaller
than that for vibrational states. Thus, a real
molecular band would be made up of many more
lines than we have shown in Figure and these
lines would be much more closely spaced.
47
 Continuum Spectra
• When solids are heated to incandescence, thermal radiation called Blackbody
Radiation is produced
• This radiation is characteristic of the temperature of the emitting surface rather than
the material composing that surface.
• Blackbody radiation is produced by the innumerable atomic and molecular oscillations
excited in the condensed solid by the thermal energy.
• Note that the energy peaks in Figure shift to shorter wavelengths with increasing
temperature. It is clear that very high temperatures are needed to cause a thermally
excited source to emit a substantial fraction of its energy as ultraviolet radiation

• Heated solids are important

sources of infrared, visible, and
longer-wavelength ultraviolet
radiation for analytical
instruments
• in the flame spectrum shown in
Figure 6-19 is probably thermal
emission from incandescent
particles in the flame. Note that
this background decreases
rapidly as the ultraviolet region
is approached.

48
 Blackbody Radiation
Wien’s Displacement Law
for blackbody radiators

Stefan-Boltzman Law
P = sT4
s = 5.6697  10-12 Wcm-2K-4

Both max and radiation power (P) are related to TEMPERATURE and current!

Eugene Hecht, Optics, Addison-Wesley, Reading, MA, 1998. 49

6C-5 Absorption of Radiation
- When radiation passes through a solid, liquid, or
gaseous sample, certain frequencies may be selectively
removed by absorption, a process in which
electromagnetic energy is transferred to the atoms, ions,
or molecules composing the sample.
- Absorption promotes these particles from their normal
room temperature state, or ground state, to one or more
higher-energy excited states.

- According to quantum theory, atoms, molecules, and ions have only

a limited number of discrete energy levels; for absorption of
radiation to occur, the energy of the exciting photon must exactly
match the energy difference between the ground state and one of
the excited states of the absorbing species.
- Since these energy differences are unique for each species, a
study of the frequencies of absorbed radiation can be used to
characterize and identify the constituents of a sample. For this
purpose, a plot of absorbance as a function of wavelength or
frequency is experimentally determined
- Typical absorption spectra are shown in Figure 6-23, reveal that
absorption spectra vary widely in appearance; some are made up
of numerous sharp peaks, while others consist of smooth
continuous curves.
- In general, the nature of a spectrum is influenced by such variables
as the complexity, the physical state, and the environment of the
absorbing species. More fundamental, however, are the differences
between absorption spectra for atoms and those for molecules 50
 Atomic Absorption
- When polychromatic ultraviolet or visible
radiation passes through a medium that consists
of monoatomic particles, such as gaseous
mercury or sodium, absorption can occur at a
few well-defined frequencies.

- The relative simplicity of such spectra is due to

the small number of possible energy states for
the absorbing particles.

- Ultraviolet and visible radiation have enough

energy to cause transitions of the outermost, or
bonding, electrons only. X-ray frequencies, on
the other hand, are several orders of magnitude
more energetic and are capable of interacting
with electrons that are closest to the nuclei of
atoms. Absorption peaks that correspond to
electronic transitions of these innermost
electrons are thus observed in the X-ray region

51
Molecular Absorption

- Absorption spectra for polyatomic

molecules are considerably more
complex than atomic spectra because
the number of energy states of
molecules are generally enormous
when compared with the number of
energy states for isolated atoms.
- The energy E associated with the
bands of a molecule is made up of
three components. That is

Number of levels/states
Eel < Evib < Erot

52
 • In contrast to atomic absorption spectra, which
consist of a series of sharp, well-defined lines,
molecular spectra in the ultraviolet and visible
regions are ordinarily characterized by absorption
regions that often encompass a substantial
wavelength range (see Figure 6-23b,c).
• Molecular absorption also involves electronic
transitions. Several closely spaced absorption
lines will be associated with each electronic
transition, because of the existence of numerous
vibrational states. Furthermore, as we have
mentioned, many rotational energy levels are
associated with each vibrational state. As a result,
the spectrum for a molecule usually consists of a
series of closely spaced absorption lines that
constitute an absorption band, such as those
shown for benzene vapor in Figure 6-23b. Unless
a high-resolution instrument is used, the individual
peaks may not be detected, and the spectra will
appear as broad smooth peaks such as those
shown in Figure 6-23c.
• Finally, in the condensed state, and in the presence of solvent molecules, the
individual lines tend to broaden even further to give nearly continuous spectra such
as that shown in Figure 6-23d. Solvent effects are considered in later chapters.
53
6C-6 Relaxation Processes
Nonradiative Relaxation
- nonradiative relaxation involves the loss of energy in a series of small steps, the
excitation energy being converted to kinetic energy by collision with other molecules.
A minute increase in the temperature of the system results.
- relaxation can also occur by emission of fluorescence radiation.

Fluorescence and Phosphorescence Emission

- Species are excited by absorption of a beam of electromagnetic radiation;
- radiant emission then occurs as the excited species return to the ground state.
- Fluorescence occurs more rapidly than phosphorescence and is generally
complete after about 10-5 s from the time of excitation. Phosphorescence emission
takes place over periods longer than 10-5 s and may indeed continue for minutes or
even hours after irradiation has ceased.
- Fluorescence and phosphorescence are most easily observed at a 90°angle to
the excitation beam.
- Resonance fluorescence describes the process in which the emitted radiation is
identical in frequency to the exciting radiation.
- Resonance fluorescence is most commonly produced by atoms in the gaseous
state, which do not have vibrational energy states superimposed on electronic
energy levels.
- Nonresonance fluorescence is caused by irradiation of molecules in solution or in
the gas phase.

54
 6C-7 The Uncertainty Principle
- first proposed in 1927 by Werner Heisenberg,
- who postulated that nature places limits on the precision with which certain pairs of physical
measurements can be made.
- The uncertainty principle, which has important and widespread implications in instrumental
analysis, can be derived from the principle of superposition, which was discussed in Section
6B-4. Applications of this principle will be found in several later chapters that deal with
spectroscopic methods.
- Let us suppose that we wish to determine the frequency n1 of a monochromatic beam of
radiation by comparing it with the output of a standard clock, which is an oscillator that
produces a light beam that has a precisely known frequency of n2. To detect and measure the
difference between the known and unknown frequencies,n n1- n2, we allow the two beams
to interfere as in Figure 6-5 and determine the time interval for a beat (A to B in Figure 6-5).
The minimum time t required to make this measurement must be equal to or greater than the
period of one beat, which as shown in Figure 6-5, is equal to 1/v. Therefore, the minimum
time for a measurement is given by
Note that to determine v with negligibly small uncertainty, a
huge measurement time is required. If the observation extends
or over a very short period, the uncertainty will be large.

Let us multiply both Meanings of the Heisenberg uncertainty principle in

sides of Eqn. by words
• If the energy E of a particle or system of particles—photons,
Planck’s constant, electrons, neutrons, or protons—is measured for an exactly
h, to give known period of time t, then this energy is uncertain by at least
h/t.
• Therefore, the energy of a particle can be known with zero
Heisenberg uncertainty only if it is observed for an infinite period. For finite
uncertainty periods, the energy measurement can never be more precise
principle. than h/ t.
55
 6D Quantitative Aspects of Spectrochemical Measurements

- there are four major classes of spectrochemical methods. All four require the measurement of
radiant power P,
- radiant power P, which is the energy of a beam of radiation that reaches a given area per
second.
- In modern instruments, radiant power is determined with a radiation detector that converts
radiant energy into an electrical signal S.
- Generally, S is a voltage or a current that ideally is directly proportional to radiant power. That is,
where , and k is a constant.

- Many detectors exhibit a small, constant response, known as a dark signal or dark response,
kd (usually a current or voltage), in the absence of radiation. In those cases, the total signal is
described by the relationship
- The dark signal is generally small and constant. Spectrochemical instruments are usually
equipped with a compensating circuit that reduces kd to zero whenever measurements are
made.

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 6D-1 Emission, Luminescence and Scattering Methods
- As shown in column 3 of Table 6-2, in emission, luminescence, and scattering
methods, the power of the radiation emitted by an analyte after excitation is
ordinarily directly proportional to the analyte concentration, c, (Pe = k.c).
- Combining this equation with Equation 6-27 gives S= k’.c (6-29)
where k’ is a constant that can be evaluated by measuring S after excitation of
one or more standards of known concentration.

6D-2 Absorption Methods - quantitative absorption methods require

two power measurements: 1) before a
beam has passed through the medium that
contains the analyte (P0) and
2) the other after passing through the
medium (P).
- Two terms, that are widely used in
absorption spectrometry and are related to
the ratio of P0 and P, are transmittance and
absorbance

a : proportionality constant called absorptivity. The

magnitude of a depends on the units used for b
and c. When the concentration in Equation 6-33 is
expressed in moles per liter and the cell length is
in centimeters, the absorptivity is called the molar
absorptivity and is given a special symbol,.
Thus, when b is in centimeters and c is in moles
per liter,  has the units L mol-1 cm-1 .
57
 Measurement of Transmittance and Absorbance

• A photometer, is used for measuring the transmittance and absorbance of aqueous

solutions with a filtered beam of visible radiation.
• The radiation from a tungsten bulb passes through a colored glass filter that restricts
the radiation to a limited band of contiguous wavelengths. The beam then passes
through a variable diaphragm that permits adjustment of the power of the radiation
that reaches the transparent cell that contains the sample. A shutter can be imposed
in front of the diaphragm that completely blocks the beam.
• With the shutter open, the radiation strikes a photoelectric transducer that converts
the radiant energy of the beam to a signal (current or voltage) that can be measured
with a digital meter as shown. 58