Raman Effect: fingerprinting the universe

At school, we were taught that Sir CV Raman won the 1930 Nobel Prize for Physics for
discovering the "Raman effect". But when we asked what exactly the Raman Effect was, our
science teacher fobbed us off, saying "it's very complicated." Clearly, even he didn't know.
Cynical students wondered why a complicated discovery without any obvious use had won the
Nobel Prize.

But today, Raman's discovery has finally become a breakthrough technology. Hand-held
scanners called Raman scanners, weighing just one-third of a kilo, are being used by US
narcotics squads and airports to detect drugs. Security experts think that Raman scanners may be
the best devices to detect explosives carried by terrorists. Safety inspectors are using Raman
scanners to detect hazardous chemicals and gases. Police forces are using Raman scanners for
forensic work.

The scanners work by detecting the molecular structure of the object they are scanning. If you
shoot a beam of light on an object, a very small part of it interacts with the atoms of the object
and scatters light in a pattern or spectrum unique to that particular molecule. This is the Raman
Effect. It is difficult to detect, and typically needs lasers to amplify the signal. Every molecule
has a different Raman pattern. This is why Raman scanning has been called the fingerprinting of
the universe: it can identify substances as surely as fingerprints can identify humans.

Identifying the chemical composition of a substance typically requires chemical and physical
tests that take time, maybe days. They typically require a sample to be extracted and destroyed
while testing. But Raman scanning can take just 20 seconds. It does not require cutting,
extracting or destroying a substance. Scanners have a laser, spectroscope and an electronic heart
that can recognize Raman patterns. This yields almost instant recognition of target substances.

For instance, narcotics squads in the US are using Raman scanners programmed to detect up to
100 drugs. At the scene of a crime, or during airport security checks, the scanner can tell whether
a substance is heroin, crack cocaine, amphetamine, or plain chalk. Security experts can
programme scanners to detect different sorts of explosives such as RDX or nitroglycerine.

For decades, Raman's discovery could not be converted into easily usable or affordable tools. In
his time, equipment for lasers and spectrum separation and scanning were primitive, bulky and
costly. Only in the 1980s did laser technology progress to the point where it was compact and
economic. This new technology was most popularly established in the CD player: a laser could
scan a disc to play music.

Scientists in many fields, including space and telecom, began to research applications for the
Raman Effect. Some found ways to enhance the Raman Effect by adding surface metals, making
the effect easier to detect. This led ultimately to the invention of scanners that could detect trace
elements of less than one part per billion. Such scanners can identify minute quantities of
bacteria, chemical pollutants, or explosive elements.

A recent article in The Atlantic, a US monthly, says that Raman scanners are gradually becoming
big business. It cites officials at Delta Nu, a manufacturer of Raman scanners, as saying that
scanners are already a $150 million business, and growing fast. The company's scanners
currently cost $15,000 each, but it hopes to cut the cost to just $5,000 in the next five to ten
years.

Researchers at UCLA and Intel have incorporated the Raman Effect on silicon. Because of its
crystalline structure, the Raman Effect is 10,000 times stronger in silicon than glass. Researchers
at JPL and Caltech have found other ways to increase laser efficiency. This has driven down size
and costs.

Researchers at Stanford University are experimenting with Raman scanners to diagnose cancers
in various organs. River Diagnostics in Rotterdam is marketing a bacteria analyzer that hospitals
can use to instantly detect deadly pathogens. One day, Raman scanners may make blood tests
obsolete: a scan may suffice to tell you the content of glucose, cholesterol, uric acid and other
elements in your blood.

Scientists aim ultimately to create a database of Raman patterns of every substance for easy
identification. This is similar to Nandan Nilekani creating a national database for fingerprints and
irises to identify every Indian. Databases have already been created for narcotics, pollutants and
explosives, which is why scanners have already become practical tools.  Every time they are
used to catch a drug smuggler or terrorist, or to detect a cancer or pollutant, we can give thanks
to CV Raman. School teachers can now teach students why exactly the Raman Effect is so
important: it fingerprints the universe.
Raman scattering
Raman scattering or the Raman effect (pronounced /ˈrɑːmən/) is the inelastic scattering of a
photon. Discovered by Sir Chandrasekhara Venkata Raman in liquids and by Grigory Landsberg
and Leonid Mandelstam in crystals.

When light is scattered from an atom or molecule, most photons are elastically scattered
(Rayleigh scattering), such that the scattered photons have the same energy (frequency) and
wavelength as the incident photons. However, a small fraction of the scattered light
(approximately 1 in 10 million photons) is scattered by an excitation, with the scattered photons
having a frequency different from, and usually lower than, the frequency of the incident photons.
In a gas, Raman scattering can occur with a change in vibrational, rotational or electronic energy
of a molecule (see energy level). Chemists are concerned primarily with the vibrational Raman
effect.
In 1922, Indian physicist C. V. Raman published his work on the "Molecular Diffraction of
Light," the first of a series of investigations with his collaborators which ultimately led to his
discovery (on 28 February 1928) of the radiation effect which bears his name. The Raman effect
was first reported by C. V. Raman and K. S. Krishnan, and independently by Grigory Landsberg
and Leonid Mandelstam, in 1928. Raman received the Nobel Prize in 1930 for his work on the
scattering of light. In 1998 the Raman Effect was designated an ACS National Historical
Chemical Landmark in recognition of its significance as a tool for analyzing the composition of
liquids, gases, and solids.

scattering Stokes and anti-Stokes

The different possibilities of visual light scattering: Rayleigh scattering (no Raman effect), Stokes
scattering (molecule absorbs energy) and anti-Stokes scattering (molecule loses energy)

There are two types of Raman scattering, Stokes scattering and anti-Stokes scattering.

The interaction of light with matter in a linear regime allows the absorption or simultaneous
emission of light precisely matching the difference in energy levels of the interacting electrons.

The Raman effect corresponds, in perturbation theory, to the absorption and subsequent emission
of a photon via an intermediate electron state, having a virtual energy level (see also: Feynman
diagram). There are three possibilities:
  no energy exchange between the incident photons and the molecules (and hence no Raman
effect)
 energy exchanges occur between the incident photons and the molecules. The energy
differences are equal to the differences of the vibrational and rotational energy-levels of the
molecule. In crystals only specific phonons are allowed (solutions of the wave equations which
do not cancel themselves) by the periodic structure, so Raman scattering can only appear at
certain frequencies. In amorphous materials like glasses, more phonons are allowed and thereby
the discrete spectral lines become broad.

 molecule absorbs energy: Stokes scattering. The resulting photon of lower energy
generates a Stokes line on the red side of the incident spectrum.
 molecule loses energy: anti-Stokes scattering. Incident photons are shifted to the blue
side of the spectrum, thus generating an anti-Stokes line.

These differences in energy are measured by subtracting the energy of the mono-energetic laser
light from the energy of the scattered photons. The absolute value, however, doesn't depend on
the process (Stokes or anti-Stokes scattering), because only the energy of the different vibrational
levels is of importance. Therefore, the Raman spectrum is symmetric relative to the Rayleigh
band. In addition, the intensities of the Raman bands are only dependent on the number of
molecules occupying the different vibrational states, when the process began. If the sample is in
thermal equilibrium, the relative numbers of molecules in states of different energy will be given
by the Boltzmann distribution:

N0: number of atoms in the lower vibrational state

N1: number of atoms in the higher vibrational state

g0: degeneracy of the lower vibrational state (number of

orbitals of the same energy)

where: g1: degeneracy of the higher vibrational state

ΔEv: energy difference between these two vibrational

states

k: Boltzmann constant

T: thermodynamic (absolute) temperature

Thus lower energy states will have more molecules in them than will higher (excited) energy
states. Therefore, the Stokes spectrum will be more intense than the anti-Stokes spectrum.
Distinction with fluorescence

The Raman effect differs from the process of fluorescence. For the latter, the incident light is
completely absorbed and the system is transferred to an excited state from which it can go to
various lower states only after a certain resonance lifetime. The result of both processes is
essentially the same: A photon with the frequency different from that of the incident photon is
produced and the molecule is brought to a higher or lower energy level. But the major difference
is that the Raman effect can take place for any frequency of the incident light. In contrast to the
fluorescence effect, the Raman effect is therefore not a resonant effect. In practice, this means
that a fluorescence peak is anchored at a specific excitation frequency, whereas a Raman peak
maintains a constant separation from the excitation frequency. Another, related distinction is that
Raman scattering is a coherent process, whereas fluorescence is not This means that the
measured intensity is the square of a coherent sum of scattering amplitudes. In practice, this
means that different paths to the excitation of the same mode may interfere, leading to Fano
effects: asymmetries in the shape of the scattering peaks.

Selection rules

The distortion of a molecule in an electric field, and therefore the vibrational Raman cross
section, is determined by its polarizability.

A Raman transition from one state to another, and therefore a Raman shift, can be activated
optically only in the presence of non-zero polarizability derivative with respect to the normal
coordinate (that is, the vibration or rotation):

Raman-active vibrations/rotations can be identified by using almost any textbook that treats
quantum mechanics or group theory for chemistry. Then, Raman-active modes can be found for
molecules or crystals that show symmetry by using the appropriate character table for that
symmetry group.
Classical Raman Physics