Spectroscopy

Radiation and Matter

Spectroscopic Methods

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 Spectroscopy
Spectroscopy studies the way
electromagnetic radiation (light) interacts
with matter as a function of frequency,
thus, it studies the energy exchange
between matter and radiation.
Traditionally, spectroscopy involved visible
light, but X-ray or IR spectroscopy are also
analytical techniques.
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 What is light?
According to Maxwell,
light is an electromagnetic
wave, caracterized by a
frequency ν or a
wavelenght λ, where νλ=c
and by a polarization.
nmedia = c/cmedia (1831-1879)

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 What is light?
Light waves are
fluctuations of the
electric and
magnetic field.
These fields are
orthogonal among
themselves and
orthogonal to the
propagation
direction.

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 What is light?
Light has characteristics of a wave,
but also of a particle.
λ=h/mv
Louis de Broglie (1925)

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 What is light?
Phenomena Waves Particles

Reflection
Refraction
Interference
Diffraction
Polarization
Photoelectric effect

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 What is light?
The light particle is called photon and its
energy (E) is given by:
E=hν=hc/λ
E [J] h [J.s] = 6.62606957×10-34 J.s
ν [Hz or s-1] c [ms -1]
λ [m] 1J = 6.241509×1018 eV

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• Gama rays Energy

• X-rays E=hν=hc/λ
• UV light
• Visible light
• Infrared light
• Microwaves
• Radio waves

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http://www.lbl.gov/MicroWorlds/ALSTool/EMSpec/EMSpec2.html

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• Nuclear transitions (Rγ) λ ∼ 0.1 Å
camadas fundamentais (RX)
o o
• Electronic transitions camadas intermédias (Far UV) A−1000 A
camadas de valência (Near UV/Vis)

vibrationa l (NIR + MIR)

• Molecular transitions 1µm−100µm
rotational (FIR)

electric spin (µ waves+ radio waves)

1mm−100m
• Spin orientations magnetic spin (radio waves)

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 Radiation Matter
Neutral or charged particles

Photons Electron
Electrons Nucleus
Ions Molecules
Neutrons Magnetic field
... ...

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Radiation – Matter

 Cross section
 Population
 Time
 Selection rules

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 Cross Section
 Interaction between radiation and matter has
an efective area of interaction, called cross
section (σ).
 The higher the interaction between radiation
and matter, the higher the cross section.
 High cross section processes present higher
interaction and small differences are more
clearly observed. Higher sensitivity.

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 Population
 If both energy levels, the upper and the lower
present the same population, then absorption
and emission have the same probability and any
spectroscopic transition is not easily observed.
 The ratio between the population of any two
energy levels separated by ∆E is given by the
Boltzmann distribution:
Nupper/Nlower = exp (- ∆E/kT)
∆E [J] k [JK-1] T [K]

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 Time
 Excitation time - 10-18 s
 Relaxation time - UV/Vis: 10-14 s
IV: 10-13 s
NMR: 10-1 - 10-8 s
Fluorescence: < 10-8 s
Phosphorescence: > 10-8 s

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 Selection rules
 Intrinsic to the quantum theory.
 Indicate which transitions are
allowed and which transitions are
forbidden.
 IR: ∆ν = ± 1 (ν=0 → ν=1)
(Overtones. Hot bands. Combinations.)

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 Energy of a Molecule

Total energy of a molecule: Etotal = Σ (Etranslation + Eelectronic + Evibration + Erotation)

Etranslation = kinetic energy, 3-D movement
Eelectronic = electronic energy, excitation of electrons: ground state → excited state
Evibration = vibrational energy, bending and stretching of covalent bonds
Erotation = rotational energy

Chemists can use ranges of the electromagnetic spectrum to

selectively manipulate the energies contained within a molecule,
to uncover detailed evidence of its chemical structure and bonding.

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 Introduction to Spectroscopy

The four most common spectroscopic methods used in organic analysis are:

Method Abbrev. Energy used Units

Ultraviolet-Visible Spectroscopy UV-Vis ultraviolet-visible nm
Infrared Spectroscopy IR infrared µm or cm-1
Nuclear Magnetic Resonance NMR radio frequencies Hz or δ
Mass Spectrometry Mass Spec electron volts amu

What actually happens to the sample during an analysis?

Question:
{How do the sample and energy “interact”?}

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 Matter/Energy Interactions
• What happens when a sample absorbs UV/Vis energy?
π*
excitation of ground state electrons UV/Vis
π → π*
(typically π and n electrons) sample transition
(∼200 nm)
Eelectronic increases momentarily
π

• What happens when a sample absorbs IR energy?

stretching and bending of bonds IR
(typically covalent bonds) -O-H - O —H
(∼3500 cm-1)
Evibration increases momentarily

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 Radiation – Matter Interaction
What happens when light interacts with a molecule?

 Absorption
 Transmission
 Emission
 Scattering
 Reflection
 Refraction

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 Radiation – Matter Interaction
• Absorption: Transition from a lower energy level to a higher
energy level by energy transfer from the incident radiation.

• Emission: Transition from a higher energy level to a lower

energy level by energy emission from the molecule.

• Scattering: Light dispersion due to interaction with matter.

Energy transfer may occur.

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 Absorption

I0 I

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 Radiation – Matter Interaction
• Transmission: Light
fraction not absorbed, T (%) = (I/I0) * 100
reflected, scattered or
refracted.
A+R+S+T = 1
A = - log10 (I/I0) = - log10 (T)
• Absorption: Transition
from a lower energy level A = log10 (1/T)
to a higher energy level
by energy transfer from
the incident radiation. (A - Absorbance)

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 Radiation – Matter Interaction

• Emission: Transition from a higher

energy level to a lower energy level by
energy emission from the molecule.

hν
hν

Absorption / Emission

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 Radiation – Matter Interaction

• Reflection: Incident light 2

component which is reflected
R ~
(n − 1)
with a reflection angle = 2
incident angle. It is a function
(n + 1)
of the refractive index n.

• Refraction: Results from the

change in the incident light n1 sen θ1 = n2 sen θ2
direction and depends on the
propagation mean.

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 Reflection / Refraccion
Incident beam Reflected beam
θ'1
θ1
meio 1 n1
meio 2 n2
θ2

Refracted beam

1626 Snell: Reflection and refraction of light.

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 Radiation – Matter Interaction

• Scattering: Change of
light direction due to
matter interaction.
Energy transfer can
occur.

Rayleigh λ-4 (Ø << λ)

Mie λ-2 (Ø ~ λ)
Tyndall λ (Ø >> λ)

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Luís Santos
XPS X-Ray X-Ray Auger
Absorption Fluorescence
e- e- Auger

FL FL FL FL

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