Definition of Absorption | Emission | Scattering

Content of the Lecture

See the contents of the first part of Light

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Absorption
It is the transition from a lower level to a higher level with
transfer of light energy from the radiation field to
receiving atoms or molecules.

Emission
It is the transition from a higher level to a lower level
where light energy is transferred to the radiation field,
or where light energy is transferred into a non-radiative decay
process (if no radiation is emitted.)

Scattering
Redirection of light due to its interaction with matter is
called scattering, and may (or may not) occur with transfer of
energy, i.e., the scattered radiation has a slightly different or the
same wavelength.

Absorption
When atoms or molecules absorb light, the incoming energy
excites a quantized structure to a higher energy level. The type of
excitation depends on the wavelength of the light.
- Electrons are promoted to higher orbital by ultraviolet or
visible light,
- Vibration is excited by infrared light,
- Rotation is excited by microwave light.
An absorption spectrum is the absorption of light as a
function of wavelength.
The spectrum of an atom or molecule depends on its
energy level structure. Absorption spectra are useful for
identifying compounds.
Measuring the concentration of an absorbing species in a
sample is accomplished by applying the Beer-Lambert Law.
The chromophore is the part of the molecule responsible for
light absorption.
Any substance that absorbs visible light will appear colored
when white light is transmitted through it or reflected from it.
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 The color of a solution is the complement of the color of
the light that it absorbs - since the substance absorbs certain
wavelengths of the white light our eyes detect the wavelengths
(colors) that are not absorbed. The unabsorbed color is called
the complement of the absorbed color.
If molecules did not absorb visible light, you could simply
flick a light on and off, and then sit back while the photons
continued to bounce around the room! Likewise, infrared light (=
heat = energy!) would not do any good in heating up your home
in the winter if it did not get absorbed by matter. Higher energy
light photons, like X-rays, tend to want to plow through more
matter before they get absorbed. (Hence, their use in medical
imaging: they can pass through your "soft" tissue, but are more
readily absorbed in your bones, which are denser.)

Absorption and chemical analysis

Each range of light corresponds to a range of frequencies (or
wavelengths) of light vibrations. Since every chemical element
has its own unique set of allowed energy levels, each element
also has its own distinctive pattern of spectral absorption (and
emission) lines!
It is the spectral "fingerprint" that astronomers use to
identify the presence of the various chemical elements in
astronomical objects. Spectral lines are what allow us, from a
"spectrum," to derive so much information about the object being
observed!
The Physics of Photosynthesis
Pigments:
Special molecule that make the mediation of light capture by
living things; they absorb wavelengths in the visible region of the
spectrum. When a pigment molecule is struck by a photon of
light, it can absorb the light energy, and thus it enters into a higher
energy level (an excited state). Each pigment absorbs (or reflects)
its own characteristic wavelengths of light. The following diagram
represents the absorption spectrum of pure chlorophyll in solution

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 - chlorophyll A (green line), and
- chlorophyll B (red line)

Chlorophylls and the Accessory Pigments

The two primary pigments involved in photosynthesis are
chlorophyll A and chlorophyll B. These two molecules
efficiently absorb light at the blue and red ends of the
spectrum when purified and in solution, and not very
efficiently in between (though this may not completely
accurately reflect the situation in living cells).
Also, in photosynthesis there is a series of pigments
(accessory pigments), covering more of the visible spectrum.
The accessory pigments act as antennae to channel the energy
they absorb into the reaction center.
A molecule of chlorophyll at the reaction center can then
transfer its excited state into bio-synthetically useful energy.

Emission
Molecules emit light to dissipate the energy of an absorbed
photon
- By emitting a photon or
- By creating heat throughout the medium
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 Atoms or molecules that are excited to high energy levels can
decay to lower levels by emitting radiation (emission or
luminescence).
Any emission of light is called luminescence
Light emitted during a chemical reaction = chemi-luminescence
For atoms excited by a high-temperature energy source
this light emission is commonly called atomic or optical
emission (see atomic-emission spectroscopy),
For atoms excited with visible light it is atomic
fluorescence, and its study is the atomic-fluorescence
spectroscopy.
(After a photon is absorbed, depending on the energy, a bond
may break and photochemistry may occur).
For molecules, chemi-luminescence is called:
- fluorescence if the transition is between states of the same
spin (short lived emission = fluorescence)
- phosphorescence if the transition occurs between states of
different spin (long-lived emission = phosphorescence)
The emission intensity of an emitting substance is linearly
proportional to analyte concentration at low concentrations,
and is useful for quantitating emitting species.

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 Scattering
When electromagnetic radiation passes through matter, most
of the radiation continues in its original direction but a small
fraction is scattered in other directions.
Light that is scattered at the same wavelength as the
incoming light is called Rayleigh scattering.
Light that is scattered in transparent solids due to vibrations
(phonons) is called Brillouin scattering, it is typically shifted by
0.1 to 1 cm-1 from the incident light.
Light that is scattered due to vibrations in molecules or
optical photons in solids is called Raman scattering. Raman
scattered light is shifted by as much as 4000 cm-1 from the
incident light.

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Beer-Lambert Law (This is a First-Order Kinetic Equation)

Introduction
Beer's law is the linear relationship between absorbance S
and concentration C of an absorbing species.

The general Beer law is usually written as:

S = ε (λ) * b * c
Where
S absorbance (dimensionless) as measured,
ε (λ) absorptivity coefficient (it is wavelength-
dependent),
b length of the pathway,
c concentration of the analyte.
When working in concentration units of molarity, the Beer
law is written as:
S=ε *b*C
Where
ε molar absorptivity coefficient with units of M-1 cm-1.
(It is wavelength-dependent)

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Instrumentation
Experimental measurements are usually made in terms of
transmittance (T), which is defined as:
T = I/Io
Where
Io initial light intensity.
I light intensity after passing through the sample.
The relation between absorbance (S) and transmittance
(T) is given by Lambert law:
S = - log T = - log (I/I o)
log (1/T) = log (I o/I )

Absorption of light by a sample

Modern absorption instruments can usually display the data

as either transmittance, %-transmittance, or absorbance.
An unknown concentration of an analyte can be
determined by measuring the amount of light that a sample
absorbs and applying Beer's law.
If the absorptivity coefficient is not known, the unknown
concentration can be determined using a working curve of
absorbance versus concentration derived from standards.

Derivation of the Beer-Lambert law

The Beer-Lambert law can be derived from an approximation
for the absorption coefficient for a molecule by approximating
the molecule by an opaque disk whose cross-sectional area, σ,
represents the effective area seen by a photon of frequency ν.
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 If the frequency of the light is far from resonance, the
area is approximately zero, and if ν is close to resonance, the
area is a maximum.

Taking an infinitesimal slab, d z, of sample:

Io intensity entering the sample at Z = 0,

Iz intensity entering the infinitesimal slab at Z = z,
dI intensity absorbed in the slab,
I intensity of light leaving the sample.
σ cross-sectional area of one molecule,
N number of molecules per cm3
A total area, cm2
Then, the total opaque area on the slab due to the absorbers is
σ*N*A*dz
The fraction of photons absorbed will be obtained by
dividing this total opaque area by the total area A
σ*N*A*dz/A ► σ * N * dz
- = σ * N * dz
- dI/Iz = σ * N * dz
- (1/Iz) dI = σ * N * dz
Integrating this equation (from Z = zero to Z = b) gives:
- ln (I / Io) = σ*N*b
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- [ln I - ln Io] = σ*N*b
l n I o - ln I = σ*N*b
Now, since concentration (C in mole/liter) could be
calculated using the number of molecules in one liter = N*1000
and Avogadro number 6.023x1023:
C in moles/liter = N in molecule/cm3 * (1000/6.023x1023)
C * 6.023 * 1023 = N*1000 in molecules/liter
C * 6.023 * 1020 = N
Hence,
l n I o - ln I = σ* N * b
l n I o - ln I = σ * C * 6.023*1020 * b
l n I o - ln I = σ * 6.023 * 1020 * b * C
As (logX = lnX/2.303) we have to divide both sides by
(2.303) to transform ln into log:
log (Io/I)= S = σ * (6.023 * 1020 / 2.303) * b * C
= σ * (2.61x1020) * b * C
= ε * b * C
log Io - log I = ε * b * C
log Io - log I = slope * C
Where ε = slope / b = σ * 2.61x1020
Plotting (log Io - log I) versus (C) gives a linear relationship
with (positive slope = ε *b) and (intercept = zero).

Typical values of molecule cross-section σ and molar absorptivity ε

σ (cm2) ε (M-1 cm-1)
Absorption by atoms 10-12 3x108
Absorption by molecules 10-16 3x104
Infrared 10-19 3x10
Raman scattering 10-29 3x10-9

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Limitations of the Beer-Lambert law in Chemical Analysis
The linearity of the Beer-Lambert law is limited by chemical
and instrumental factors.
Beer's law shows us that absorbance (A) is proportional to
the concentration (c) of the absorbing species. It works very
well for dilute solutions ( 0.01 M) of most substances. As a
solution becomes more concentrated, solute molecules begin to
influence each other as a result of their close proximity.
In concentrated solutions, the properties of each molecule
(including the absorption of light) are likely to change
result: a graph of absorbance (A) vs concentration (c) is no
longer a straight line
Another factor affecting the linearity of Beer's law:
The possibility that a non-absorbing solute in a solution is
interacting with the absorbing species - this can affect the
apparent absorptivity

Causes of non-linearity include:

• deviations in absorptivity coefficients at high concentrations
(>0.01M) due to electrostatic interactions between molecules
in close proximity.
• scattering of light due to suspended particulates in the sample
• fluorescence or phosphorescence of the sample.
• changes in refractive index at high analyte concentration.
• shifts in chemical equilibria as a function of concentration.
• non-monochromatic radiation, deviations can be minimized
by using a relatively flat part of the absorption spectrum such
as the maximum of an absorption band.
• stray light.

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