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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

• 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. Brillouin scattering 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 phonons in solids is called Raman scattering.
Raman scattered light is shifted by as much as 4000 cm-1 from the incident light.

Now - Let’s learn about some uses of Spectroscopy…..

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Atomic spectroscopy

Atomic Transitions – Theory

The probability that an atomic


spectroscopic transition will occur is
called the transition probability or
transition strength. This probability will
determine the extent to which an atom will
absorb light at a resonance frequency, and
the intensity of the emission lines from an
atomic excited state. The spectral width of
a spectroscopic transition depends on the
widths of the initial and final states. The
width of the ground state is essentially a
delta function and the width of an excited
state depends on its lifetime.

Atomic-Absorption Spectroscopy

Atomic-absorption (AA) spectroscopy uses the absorption of light to measure the


concentration of gas-phase atoms. Since samples are usually liquids or solids, the analyte
atoms or ions must be vaporized in a flame or graphite furnace. The atoms absorb
ultraviolet or visible light and make transitions to higher electronic energy levels. The
analyte concentration is determined from the amount of absorption. Applying the Beer-
Lambert law directly in AA spectroscopy is difficult due to variations in the atomization
efficiency from the sample matrix, and nonuniformity of concentration and path length of
analyte atoms (in graphite furnace AA). Concentration measurements are usually
determined from a working curve after calibrating the instrument with standards of
known concentration.

Schematic of an atomic-absorption experiment

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Atomic Emission Spectroscopy

Atomic emission spectroscopy (AES or OES [optical emission spectroscopy]) uses


quantitative measurement of the optical emission from excited atoms to determine
analyte concentration. Analyte atoms in solution are aspirated into the excitation region
where they are desolvated, vaporized, and atomized by a flame, discharge, or plasma.
These high-temperature atomization sources provide sufficient energy to promote the
atoms into high energy levels. The atoms decay back to lower levels by emitting light.
Since the transitions are between distinct atomic energy levels, the emission lines in the
spectra are narrow. The spectra of samples containing many elements can be very
congested, and spectral separation of nearby atomic transitions requires a high-resolution
spectrometer. Since all atoms in a sample are excited simultaneously, they can be
detected simultaneously using a polychromator with multiple detectors. This ability to
simultaneously measure multiple elements is a major advantage of AES compared to
atomic-absorption (AA) spectroscopy.

Schematic of an AES experiment

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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Infrared (IR) absorption spectroscopy

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).

Infrared Absorption Bands


IR absorption spectroscopy uses mid-infrared light (2.5 - 50 ?m, 4000 - 200 cm-1) to
detect specific types of chemical bonds in a sample for identification of organic and
organometallic molecules. There are two regions in IR absorption spectra: the "functional
group region" and the "fingerprint region". The functional group region spans from 4000
to 1300 cm-1. In this region the bands are characteristic of specific functional groups in a
molecule. The fingerprint region spans from 1300 to 900 cm-1. In this portion of the
spectrum the energy of the absorption bands varies depending on the structure of a
molecule.

Table of characteristic IR bands

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.

Group Bond Approx. Energy (cm-1)


hydroxyl O-H 3610-3640
amines N-H 3300-3500
aromatic rings C-H 3000-3100
alkenes C-H 3020-3080
alkanes C-H 2850-2960
nitriles C N 2210-2260
carbonyl C=O 1650-1750
amines C-N 1180-1360

Electron spectroscopy
Introduction

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Electron spectroscopies analyze the electrons that are ejected from


a material for qualitative or semi-quantitative analysis. In general
an excitation source such as X-rays or electrons will eject an
electron from an inner-shell orbital of an atom. Detecting
photoelectrons that are ejected by X-rays is call X-ray
photoelectron spectroscopy (XPS) or electron spectroscopy for
chemical analysis (ESCA). Detecting electrons that are ejected
from higher orbitals to conserve energy during electron transitions
is called Auger electron spectroscopy (AES). These electron
processes are described below. Ejected electrons can escape only
from a depth of approximately 3 nm or less, making electron
spectroscopy most useful to study surfaces of solid materials.
Depth profiling is accomplished by combining an electron
spectroscopy with a sputtering source that removes surface layers.

Auger Electron Spectroscopy

Auger (pronounced ~o-jay) electron spectroscopy is an electron spectroscopic method


that uses a beam of electrons to knock electrons out of inner-shell orbitals. Auger
electrons are ejected to conserve energy when electrons in higher shells fill the vacancy
in the inner shell. These Auger electrons have energies characteristic of the emitting atom
due to the characteristic energy-level structure of that element.

X-ray Photoelectron Spectroscopy


X-ray photoelectron spectroscopy (XPS, also called Energy-level diagram for XPS
electron spectroscopy for chemical analysis, ESCA) is
a electron spectroscopic method that uses X-rays to
eject electrons from inner-shell orbitals. The kinetic
energy, Ek, of these photoelectrons is determined by
the energy of the X-ray radiation, h , and the
electron binding energy, Eb, as given by:

Ek = h - Eb

The experimentally measured energies of the


photoelectrons are given by:

Ek = h - Eb - Ew

where Ew is the work function of the spectrometer.

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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.

Near-Infrared Absorption Spectroscopy

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

Anisotropic crystalline solids, and


samples containing an excess of
one enantiomer of a chiral
molecule, can rotate the orientation
of plane-polarized light. Such
substances are said to have optical
activity. Measurement of this
change in polarization orientation
is called polarimetry, and the
measuring instrument is called a
polarimeter. These measurements
are useful for studying the
structure of anisotropic materials,
and for checking the purity of
chiral mixtures. A sample that
contains only one enantiomer of a
chiral molecule is said to be optically pure. The enantiomer that rotates light to the right,
or clockwise when viewing in the direction of light propagation, is called the
dextrorotatory (d) or (+) enantiomer, and the enantiomer that rotates light to the left, or
counterclockwise, is called the levorotatory (l) or (-) enantiomer.

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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.

Linearly or plane-polarized light is the superposition of equal intensities of left- and


right-circularly polarized light. As plane-polarized light travels through an optically
active sample, the left- and right-circularly polarized components travel at different
velocities. This difference in velocities creates a phase shift between the two circularly
polarized components when they exit the sample. Summing the two components still
produces linearly polarized light, but at a different orientation from the light entering the
sample.

Ultraviolet and Visible Absorption Spectroscopy

Ultraviolet and visible (UV-Vis) absorption spectroscopy is the measurement of the


attenuation of a beam of light after it passes through a sample or after reflection from a
sample surface. Absorption measurements can be at a single wavelength or over an
extended spectral range. Ultraviolet and visible light are energetic enough to promote
outer electrons to higher energy levels, and UV-Vis spectroscopy is usually applied to
molecules or inorganic complexes in solution. The UV-Vis spectra have broad features
that are of limited use for sample identification but are very useful for quantitative
measurements. The concentration of an analyte in solution can be determined by
measuring the absorbance at some wavelength and applying the Beer-Lambert Law.

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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Nuclear and electron resonance spectroscopies

Electron Paramagnetic Resonance Spectroscopy

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.

Electron-paramagnetic-resonance (EPR) or electron-spin-resonance (ESR) spectroscopy


measures the absorption of microwave radiation by an unpaired electron when it is placed
in a strong magnetic field.

Species that contain unpaired electrons:

1. Free radicals
2. Odd electron molecules
3. Transition-metal complexes
4. Lanthanide ions
5. Triplet-state molecule

Nuclear Magnetic Resonance (NMR) Spectroscopy

Nuclear magnetic resonance (NMR) spectroscopy uses radiofrequency radiation to


induce transitions between different nuclear spin states of samples in a magnetic field.
NMR spectroscopy can be used for quantitative measurements, but it is most useful for
determining the structure of molecules (along with IR spectroscopy and mass
spectrometry). The utility of NMR spectroscopy for structural characterization arises
because different atoms in a molecule experience slightly different magnetic fields and
therefore transitions at slightly different resonance frequencies in an NMR spectrum.
Furthermore, splittings of the spectra lines arise due to interactions between different
nuclei, which provides information about the proximity of different atoms in a molecule.

• Continuous-Wave Nuclear Magnetic Resonance (NMR) Spectroscopy

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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• Fourier-Transform Nuclear Magnetic Resonance (FT-NMR) Spectroscopy

Fourier-transform NMR spectrometers use a pulse of radiofrequency (RF)


radiation to cause nuclei in a magnetic field to flip into the higher-energy
alignment. Due to the Heisenberg uncertainty principle, the frequency width of
the RF pulse (typically 1-10 ?s) is wide enough to simultaneously excite nuclei in
all local environments. All of the nuclei will re-emit RF radiation at their
respective resonance frequencies, creating an interference pattern in the resulting
RF emission versus time, known as a free-induction decay (FID). The frequencies
are extracted from the FID by a Fourier transform of the time-based data.

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X-ray and gamma-ray spectroscopies

Extended X-ray Absorption Fine Structure

Extended X-ray Absorption Fine Structure (EXAFS)


occurs due to interference effects as photoelectrons
leave the surface of a material. The interference
depends on the interatomic distance between the atom
that ejected the photoelectron and the nearest
neighbor atom, and to lesser extents the next nearest
neighbor and other atoms. EXAFS therefore provides
a means to determine the structure of the atoms on the
surface of a material. The fine structure appears as a
modulation on the absorption edge, and requires sophisticated modeling to extract the
structural information about the sample surface. The most common source for
EXAFS is synchrotron radiation, which provides an intense and tunable source of X-
rays.

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.

Production of gamma rays for 57Fe Mossbauer spectroscopy

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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

X-ray fluorescence is a spectroscopic method that is commonly used for solids in


which secondary X-ray emission is generated by excitation of a sample with X-rays.
The X-rays eject inner-shell electrons. Outer-shell electrons take their place and emit
photons in the process. The wavelength of the photons depends on the energy
difference between the outer-shell and inner-shell electron orbitals. The amount of X-
ray fluorescence is very sample dependent and quatitative analysis requires
calibration with standards that are similar to the sample matrix.

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Laser spectroscopy

Cavity-Ringdown Laser Absorption Spectroscopy

Cavity-ringdown laser absorption spectroscopy (CRLAS) is an


ultrasensitive method to make quantitative absorption
measurements of very low concentrations of analytes. The
technique uses a laser pulse that is reflected back and forth
between two highly reflecting mirrors. This procedure results in
a very long path length, to which the measured absorbance is
directly proportional as described by the Beer-Lambert law.

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

Intracavity-absorption spectroscopy is an ultrasensitive method for measuring very small


absorptions. Some examples are very low concentrations of analytes, and very weak
absorption such as infrared overtone bands. The technique takes advantage of the very
high light intensities within a laser resonance cavity, and the sensitivity of the lasing
output to losses within the cavity. Small losses within the laser cavity due to absorption
results in large changes in the intensity of the laser output.

Schematic of an intracavity-absorption experiment

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Raman Spectroscopy

Raman spectroscopy is the measurement of the


wavelength and intensity of inelastically scattered
light from molecules. The Raman scattered light
occurs at wavelengths that are shifted from the
incident light by the energies of molecular
vibrations. The mechanism of Raman scattering is
different from that of infrared absorption, and
Raman and IR spectra provide complementary
information. Typical applications are in structure
determination, multicomponent qualitative analysis,
and quantitative analysis.

Resonance-Ionization Spectroscopy

Resonance-ionization spectroscopy (RIS) is a spectroscopic method that uses resonant


laser excitation to promote an atom or molecule above its ionization potential to create an
ion. The ions are detected as a current by a biased collector or by a mass spectrometer.
RIS is useful to study the electronic structure of atoms or molecules and to make
quantitative measurements of analyte concentrations

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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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