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Introduction..........................................................................................................3
Atomic spectroscopy...........................................................................................5
Infrared (IR) absorption spectroscopy.................................................................7
Electron spectroscopy.........................................................................................7
Molecular spectroscopies....................................................................................9
Nuclear and electron resonance spectroscopies..............................................11
X-ray and gamma-ray spectroscopies..............................................................13
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Introduction
Spectroscopy is the use of the absorption, emission, or scattering of electromagnetic
radiation by matter to qualitatively or quantitatively study the matter or to study physical
processes. The matter can be atoms, molecules, atomic or molecular ions, or solids. The
interaction of radiation with matter can cause redirection of the radiation and/or
transitions between the energy levels of the atoms or molecules.
Absorption
• Matter can capture electromagnetic radiation and convert the energy of a photon
to internal energy. This process is called absorption. Energy is transferred from
the radiation field to the absorbing species. We describe the energy change of the
absorber as a transition or an excitation from a lower energy level to a higher
energy level. Since the energy levels of matter are quantized, only light of energy
that can cause transitions from one level to another will be absorbed.
• The type of excitation depends on the wavelength of the light. Electrons are
promoted to higher orbitals by ultraviolet or visible light, vibrations are excited by
infrared light, and rotations are excited by microwaves. Absorption spectroscopy
is one way to study the energy levels of the atoms, molecules, and solids. 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, making
absorption spectra useful for identifying compounds.
• Measuring the concentration of an absorbing species in a sample is accomplished
by applying the Beer-Lambert Law.
Emission
• Atoms, molecules, or solids that are excited to high energy levels can decay to
lower levels by emitting radiation (emission or luminescence). For atoms excited
by a high-temperature energy source this light emission is commonly called
atomic or optical emission (see atomic-emission spectroscopy) and for atoms
excited with light it is called atomic fluorescence (see atomic-fluorescence
spectroscopy). For molecules it is called fluorescence if the transition is between
states of the same spin and phosphorescence if the transition occurs between
states of different spin. Separate documents describe molecular fluorescence,
which can be done with compact instruments, and laser-induced fluorescence.
• The emission intensity of an emitting substance is linearly proportional to analyte
concentration at low concentrations. Atomic emission and molecular fluorescence
are therefore useful for quantitating emitting species.
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Scattering
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Atomic spectroscopy
Atomic-Absorption Spectroscopy
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Atomic-Fluorescence Spectroscopy
Atomic fluorescence is the optical emission from gas-phase atoms that have been excited
to higher energy levels by absorption of electromagnetic radiation. The main advantage
of fluorescence detection compared to absorption measurements is the greater sensitivity
achievable because the fluorescence signal has a very low background. The resonant
excitation provides selective excitation of the analyte to avoid interferences. AFS is
useful to study the electronic structure of atoms and to make quantitative measurements.
Analytical applications include flames and plasmas diagnostics, and enhanced sensitivity
in atomic analysis.
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Introduction
Infrared (IR) absorption spectroscopy is the measurement of the wavelength and intensity
of the absorption of mid-infrared light by a sample. Mid-infrared light (2.5 - 50 ?m, 4000
- 200 cm-1) is energetic enough to excite molecular vibrations to higher energy levels. The
wavelength of many IR absorption bands are characteristic of specific types of chemical
bonds, and IR spectroscopy finds its greatest utility for qualitative analysis of organic and
organometallic molecules. IR spectroscopy is used to confirm the identify of a particular
compound and as a tool to help determine the structure of a newly synthesized molecule
(with NMR spectroscopy and mass spectrometry).
The following table lists some of the more common functional groups and their
characteristic IR absorption energy. More extensive tables can be found in organic
chemistry texts and other reference sources.
Electron spectroscopy
Introduction
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Ek = h - Eb
Ek = h - Eb - Ew
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Molecular spectroscopies
Introduction
The bonding of atoms to form molecules or solids changes the orbitals that electrons can
occupy, and therefore also changes the energies of the electrons. Bonded atoms also can
vibrate and the vibrations will have quantized energy states. Molecules in the gas phase
or in solution can rotate, which just like vibrations will have definite rotational energy
states.
NIR spectroscopy is the measurement of the wavelength and intensity of the absorption
of near-infrared light by a sample. Near-infrared light spans the 800 nm - 2.5 ?m (12,500
- 4000 cm-1) range and is energetic enough to excite overtones and combinations of
molecular vibrations to higher energy levels. NIR spectroscopy is typically used for
quantitative measurement of organic functional groups, especially O-H, N-H, and C=O.
Detection limits are typically 0.1% and applications include pharmaceutical, agricultural,
polymer, and clinical analysis.
Polarimetry
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Optical rotation occurs because optically active samples have different refractive indices
for left- and right-circularly polarized light. Another way to make this statement is that
left- and right-circularly polarized light travel through an optically active sample at
different velocities. This condition occurs because a chiral center has a specific geometric
arrangement of four different substituents, each of which has a different electronic
polarizability. Light travels through matter by interacting with the electron clouds that are
present. Left-circularly polarized light therefore interacts with an anisotropic medium
differently than does right-circularly polarized light.
Since the UV-Vis range spans the range of human visual acuity of approximately 400 -
750 nm, UV-Vis spectroscopy is useful to characterize the absorption, transmission, and
reflectivity of a variety of technologically important materials, such as pigments,
coatings, windows, and filters. This more qualitative application usually requires
recording at least a portion of the UV-Vis spectrum for characterization of the optical or
electronic properties of materials.
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When an atom or molecule with an unpaired electron is placed in a magnetic field, the
spin of the unpaired electron can align either in the same direction or in the opposite
direction as the field. These two electron alignments have different energies and
application of a magnetic field to an unpaired electron lifts the degeneracy of the ?1/2
spins of the electron.
1. Free radicals
2. Odd electron molecules
3. Transition-metal complexes
4. Lanthanide ions
5. Triplet-state molecule
Continuous-wave NMR spectrometers have largely been replaced with pulsed FT-
NMR instruments. However due to the lower maintenance and operating cost of
cw instruments, they are still commonly used for routine 1H NMR spectroscopy at
60 MHz. (Low-resolution cw instruments require only water-cooled
electromagnets instead of the liquid-He-cooled superconducting magnets found in
higher-field FT-NMR spectrometers.)
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Mossbauer Spectroscopy
The Mossbauer effect is the recoil-free emission of gamma radiation from a solid
radioactive material. Since the gamma emission is recoil-free, it can be resonantly
absorbed by stationary atoms, i.e., also in a solid. The nuclear transitions are very
sensitive to the local environment of the atom and Mossbauer spectroscopy is a sensitive
probe of the different environments an atom occupies in a solid material.
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Approximately 90% of the 57Fe nuclear excited state decays through the intermediate
level to produce 14.4 keV gamma radiation. These gamma photons can then be absorbed
by 57Fe in a sample.
X-ray Fluorescence
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Laser spectroscopy
An optical detector is placed behind one of the mirrors to detect the small amount of the
light that passes through the mirror. With no absorbing analyte present, the laser pulse
will decrease in intensity after each round trip due to the loss of light through the
monitoring mirror and other losses. When an absorbing species is present between the
mirrors, the intensity of the laser pulse decreases more rapidly. The analyte concentration
is determined by calibrating this decay time with known concentration of analyte.
Intracavity-Absorption Spectroscopy
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Raman Spectroscopy
Resonance-Ionization Spectroscopy
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ביבליוגרפיה:
ספרות:
1. R. Bevinson, "Modern Chemical Techniques"
2. “Introduction to Spectroscopy”, by Donald L. Pavia, Gary M. Lampman,
George S. Kriz
אתרים:
1. science.uniserve.edu.au
2. www.colby.edu/chemistry/PChem
3. www.spectroscopynow.com
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