2 - Spectroscopy Introduction
2 - Spectroscopy Introduction
2 - Spectroscopy Introduction
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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)
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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
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Introduction to Spectroscopy
The four most common spectroscopic methods used in organic analysis are:
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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
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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.
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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
hν
hν
Absorption / Emission
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Radiation – Matter Interaction
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Reflection / Refraccion
Incident beam Reflected beam
θ'1
θ1
meio 1 n1
meio 2 n2
θ2
Refracted beam
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Radiation – Matter Interaction
• Scattering: Change of
light direction due to
matter interaction.
Energy transfer can
occur.
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XPS X-Ray X-Ray Auger
Absorption Fluorescence
e- e- Auger
FL FL FL FL
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