Raman spectroscopy

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Energy-level diagram showing the states involved in Raman spectra.

Raman spectroscopy (/ˈrɑːmən/); (named after Indian physicist C. V. Raman) is a
spectroscopic technique typically used to determine vibrational modes of molecules,
although rotational and other low-frequency modes of systems may also be observed.
[1] Raman spectroscopy is commonly used in chemistry to provide a structural
fingerprint by which molecules can be identified.

Raman spectroscopy relies upon inelastic scattering of photons, known as Raman

scattering. A source of monochromatic light, usually from a laser in the visible,
near infrared, or near ultraviolet range is used, although X-rays can also be used.
The laser light interacts with molecular vibrations, phonons or other excitations
in the system, resulting in the energy of the laser photons being shifted up or
down. The shift in energy gives information about the vibrational modes in the
system. Infrared spectroscopy typically yields similar yet complementary
information.

Typically, a sample is illuminated with a laser beam. Electromagnetic radiation

from the illuminated spot is collected with a lens and sent through a
monochromator. Elastic scattered radiation at the wavelength corresponding to the
laser line (Rayleigh scattering) is filtered out by either a notch filter, edge
pass filter, or a band pass filter, while the rest of the collected light is
dispersed onto a detector.

Spontaneous Raman scattering is typically very weak; as a result, for many years
the main difficulty in collecting Raman spectra was separating the weak
inelastically scattered light from the intense Rayleigh scattered laser light
(referred to as "laser rejection"). Historically, Raman spectrometers used
holographic gratings and multiple dispersion stages to achieve a high degree of
laser rejection. In the past, photomultipliers were the detectors of choice for
dispersive Raman setups, which resulted in long acquisition times. However, modern
instrumentation almost universally employs notch or edge filters for laser
rejection. Dispersive single-stage spectrographs (axial transmissive (AT) or
Czerny–Turner (CT) monochromators) paired with CCD detectors are most common
although Fourier transform (FT) spectrometers are also common for use with NIR
lasers.

The name "Raman spectroscopy" typically refers to vibrational Raman using laser
wavelengths which are not absorbed by the sample. There are many other variations
of Raman spectroscopy including surface-enhanced Raman, resonance Raman, tip-
enhanced Raman, polarized Raman, stimulated Raman, transmission Raman, spatially-
offset Raman, and hyper Raman.

Contents
1 Theory
2 History
3 Raman shift
4 Instrumentation
4.1 Lasers
4.2 Detectors
4.2.1 Detectors for dispersive Raman
4.2.2 Detectors for FT–Raman
4.3 Filters
5 Applications
5.1 Art and cultural heritage
6 Microspectroscopy
7 Polarization dependence of Raman scattering
7.1 Characterization of the symmetry of a vibrational mode
8 Variants
8.1 Spontaneous (or far-field) Raman spectroscopy
8.2 Enhanced (or near-field) Raman spectroscopy
8.3 Non-linear Raman spectroscopy
8.4 Morphologically-Directed Raman spectroscopy
9 References
10 Further reading
11 External links
Theory
Main article: Raman scattering

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The magnitude of the Raman effect correlates with polarizability of the electrons
in a molecule. It is a form of inelastic light scattering, where a photon excites
the sample. This excitation puts the molecule into a virtual energy state for a
short time before the photon is emitted. Inelastic scattering means that the energy
of the emitted photon is of either lower or higher energy than the incident photon.
After the scattering event, the sample is in a different rotational or vibrational
state.

For the total energy of the system to remain constant after the molecule moves to a
new rovibronic (rotational-vibrational-electronic) state, the scattered photon
shifts to a different energy, and therefore a different frequency. This energy
difference is equal to that between the initial and final rovibronic states of the
molecule. If the final state is higher in energy than the initial state, the
scattered photon will be shifted to a lower frequency (lower energy) so that the
total energy remains the same. This shift in frequency is called a Stokes shift, or
downshift. If the final state is lower in energy, the scattered photon will be
shifted to a higher frequency, which is called an anti-Stokes shift, or upshift.

For a molecule to exhibit a Raman effect, there must be a change in its electric
dipole-electric dipole polarizability with respect to the vibrational coordinate
corresponding to the rovibronic state. The intensity of the Raman scattering is
proportional to this polarizability change. Therefore, the Raman spectrum
(scattering intensity as a function of the frequency shifts) depends on the
rovibronic states of the molecule.

The Raman effect is based on the interaction between the electron cloud of a sample
and the external electric field of the monochromatic light, which can create an
induced dipole moment within the molecule based on its polarizability. Because the
laser light does not excite the molecule there can be no real transition between
energy levels.[2] The Raman effect should not be confused with emission
(fluorescence or phosphorescence), where a molecule in an excited electronic state
emits a photon and returns to the ground electronic state, in many cases to a
vibrationally excited state on the ground electronic state potential energy
surface. Raman scattering also contrasts with infrared (IR) absorption, where the
energy of the absorbed photon matches the difference in energy between the initial
and final rovibronic states. The dependence of Raman on the electric dipole-
electric dipole polarizability derivative also differs from IR spectroscopy, which
depends on the electric dipole moment derivative, the atomic polar tensor (APT).
This contrasting feature allows rovibronic transitions that might not be active in
IR to be analyzed using Raman spectroscopy, as exemplified by the rule of mutual
exclusion in centrosymmetric molecules. Transitions which have large Raman
intensities often have weak IR intensities and vice versa. If a bond is strongly
polarized, a small change in its length such as that which occurs during a
vibration has only a small resultant effect on polarization. Vibrations involving
polar bonds (e.g. C-O , N-O , O-H) are therefore, comparatively weak Raman
scatterers. Such polarized bonds, however, carry their electrical charges during
the vibrational motion, (unless neutralized by symmetry factors), and this results
in a larger net dipole moment change during the vibration, producing a strong IR
absorption band. Conversely, relatively neutral bonds (e.g. C-C , C-H , C=C) suffer
large changes in polarizability during a vibration. However, the dipole moment is
not similarly affected such that while vibrations involving predominantly this type
of bond are strong Raman scatterers, they are weak in the IR. A third vibrational
spectroscopy technique, inelastic incoherent neutron scattering (IINS), can be used
to determine the frequencies of vibrations in highly symmetric molecules that may
be both IR and Raman inactive. The IINS selection rules, or allowed transitions,
differ from those of IR and Raman, so the three techniques are complementary. They
all give the same frequency for a given vibrational transition, but the relative
intensities provide different information due to the different types of interaction
between the molecule and the incoming particles, photons for IR and Raman, and
neutrons for IINS.

History
Although the inelastic scattering of light was predicted by Adolf Smekal in 1923,
[3] it was not observed in practice until 1928. The Raman effect was named after
one of its discoverers, the Indian scientist C. V. Raman, who observed the effect
in organic liquids in 1928 together with K. S. Krishnan, and independently by
Grigory Landsberg and Leonid Mandelstam in inorganic crystals.[1] Raman won the
Nobel Prize in Physics in 1930 for this discovery. The first observation of Raman
spectra in gases was in 1929 by Franco Rasetti.[4]

Systematic pioneering theory of the Raman effect was developed by Czechoslovak

physicist George Placzek between 1930 and 1934.[5] The mercury arc became the
principal light source, first with photographic detection and then with
spectrophotometric detection.

In the years following its discovery, Raman spectroscopy was used to provide the
first catalog of molecular vibrational frequencies. Typically, the sample was held
in a long tube and illuminated along its length with a beam of filtered
monochromatic light generated by a gas discharge lamp. The photons that were
scattered by the sample were collected through an optical flat at the end of the
tube. To maximize the sensitivity, the sample was highly concentrated (1 M or more)
and relatively large volumes (5 mL or more) were used.

Raman shift
Raman shifts are typically reported in wavenumbers, which have units of inverse
length, as this value is directly related to energy. In order to convert between
spectral wavelength and wavenumbers of shift in the Raman spectrum, the following
formula can be used:

{\displaystyle \Delta {\tilde {\nu }}=\left({\frac {1}{\lambda _{0}}}-{\frac {1}

{\lambda _{1}}}\right)\ ,}{\displaystyle \Delta {\tilde {\nu }}=\left({\frac {1}
{\lambda _{0}}}-{\frac {1}{\lambda _{1}}}\right)\ ,}
where {\displaystyle \Delta {\tilde {\nu }}}{\displaystyle \Delta {\tilde {\nu }}}
is the Raman shift expressed in wavenumber, {\displaystyle \lambda _{0}}\lambda
_{0} is the excitation wavelength, and {\displaystyle \lambda _{1}}\lambda _{1} is
the Raman spectrum wavelength. Most commonly, the unit chosen for expressing
wavenumber in Raman spectra is inverse centimeters (cm−1). Since wavelength is
often expressed in units of nanometers (nm), the formula above can scale for this
unit conversion explicitly, giving
{\displaystyle \Delta {\tilde {\nu }}({\text{cm}}^{-1})=\left({\frac {1}{\lambda
_{0}({\text{nm}})}}-{\frac {1}{\lambda _{1}({\text{nm}})}}\right)\times {\frac
{(10^{7}{\text{nm}})}{({\text{cm}})}}.}{\displaystyle \Delta {\tilde {\nu }}
({\text{cm}}^{-1})=\left({\frac {1}{\lambda _{0}({\text{nm}})}}-{\frac {1}{\lambda
_{1}({\text{nm}})}}\right)\times {\frac {(10^{7}{\text{nm}})}{({\text{cm}})}}.}
Instrumentation

An early Raman spectrum of benzene published by Raman and Krishnan.[6]

Schematic of one possible dispersive Raman spectroscopy setup.[7]

Modern Raman spectroscopy nearly always involves the use of lasers as excitation
light sources. Because lasers were not available until more than three decades
after the discovery of the effect, Raman and Krishnan used a mercury lamp and
photographic plates to record spectra. Early spectra took hours or even days to
acquire due to weak light sources, poor sensitivity of the detectors and the weak
Raman scattering cross-sections of most materials. Various colored filters and
chemical solutions were used to select certain wavelength regions for excitation
and detection but the photographic spectra were still dominated by a broad center
line corresponding to Rayleigh scattering of the excitation source.[8]

Technological advances have made Raman spectroscopy much more sensitive,

particularly since the 1980s. The most common modern detectors are now charge-
coupled devices (CCDs). Photodiode arrays and photomultiplier tubes were common
prior to the adoption of CCDs. The advent of reliable, stable, inexpensive lasers
with narrow bandwidths has also had an impact.[9]

Lasers
Raman spectroscopy requires a light source such as a laser. The resolution of the
spectrum relies on the bandwidth of the laser source used.[10] Generally shorter
wavelength lasers give stronger Raman scattering due to the ν4 increase in Raman
scattering cross-sections, but issues with sample degradation or fluorescence may
result.[9]

Continuous wave lasers are most common for normal Raman spectroscopy, but pulsed
lasers may also be used. These often have wider bandwidths than their CW
counterparts but are very useful for other forms of Raman spectroscopy such as
transient, time-resolved and resonance Raman.[10][11]

Detectors
Raman scattered light is typically collected and either dispersed by a spectrograph
or used with an interferometer for detection by Fourier Transform (FT) methods. In
many cases commercially available FT-IR spectrometers can be modified to become FT-
Raman spectrometers.[9]

Detectors for dispersive Raman

In most cases, modern Raman spectrometers use array detectors such as CCDs. Various
types of CCDs exist which are optimized for different wavelength ranges.
Intensified CCDs can be used for very weak signals and/or pulsed lasers.[9][12] The
spectral range depends on the size of the CCD and the focal length of spectrograph
used.[13]

It was once common to use monochromators coupled to photomultiplier tubes. In this

case the monochromator would need to be moved in order to scan through a spectral
range.[9]

Detectors for FT–Raman

FT–Raman is almost always used with NIR lasers and appropriate detectors must be
used depending on the exciting wavelength. Germanium or Indium gallium arsenide
(InGaAs) detectors are commonly used.[9]
Filters
It is usually necessary to separate the Raman scattered light from the Rayleigh
signal and reflected laser signal in order to collect high quality Raman spectra
using a laser rejection filter. Notch or long-pass optical filters are typically
used for this purpose. Before the advent of holographic filters it was common to
use a triple-grating monochromator in subtractive mode to isolate the desired
signal.[9] This may still be used to record very small Raman shifts as holographic
filters typically reflect some of the low frequency bands in addition to the
unshifted laser light. However, Volume hologram filters are becoming more common
which allow shifts as low as 5 cm−1 to be observed.[14][15][16]

Applications
Raman spectroscopy is used in chemistry to identify molecules and study chemical
bonding and intramolecular bonds. Because vibrational frequencies are specific to a
molecule's chemical bonds and symmetry (the fingerprint region of organic molecules
is in the wavenumber range 500–1,500 cm−1),[17] Raman provides a fingerprint to
identify molecules. For instance, Raman and IR spectra were used to determine the
vibrational frequencies of SiO, Si2O2, and Si3O3 on the basis of normal coordinate
analyses.[18] Raman is also used to study the addition of a substrate to an enzyme.

In solid-state physics, Raman spectroscopy is used to characterize materials,

measure temperature, and find the crystallographic orientation of a sample. As with
single molecules, a solid material can be identified by characteristic phonon
modes. Information on the population of a phonon mode is given by the ratio of the
Stokes and anti-Stokes intensity of the spontaneous Raman signal. Raman
spectroscopy can also be used to observe other low frequency excitations of a
solid, such as plasmons, magnons, and superconducting gap excitations. Distributed
temperature sensing (DTS) uses the Raman-shifted backscatter from laser pulses to
determine the temperature along optical fibers. The orientation of an anisotropic
crystal can be found from the polarization of Raman-scattered light with respect to
the crystal and the polarization of the laser light, if the crystal structure’s
point group is known.

In nanotechnology, a Raman microscope can be used to analyze nanowires to better

understand their structures, and the radial breathing mode of carbon nanotubes is
commonly used to evaluate their diameter.

Raman active fibers, such as aramid and carbon, have vibrational modes that show a
shift in Raman frequency with applied stress. Polypropylene fibers exhibit similar
shifts.

In solid state chemistry and the bio-pharmaceutical industry, Raman spectroscopy

can be used to not only identify active pharmaceutical ingredients (APIs), but to
identify their polymorphic forms, if more than one exist. For example, the drug
Cayston (aztreonam), marketed by Gilead Sciences for cystic fibrosis,[19] can be
identified and characterized by IR and Raman spectroscopy. Using the correct
polymorphic form in bio-pharmaceutical formulations is critical, since different
forms have different physical properties, like solubility and melting point.

Raman spectroscopy has a wide variety of applications in biology and medicine. It

has helped confirm the existence of low-frequency phonons[20] in proteins and DNA,
[21][22][23][24] promoting studies of low-frequency collective motion in proteins
and DNA and their biological functions.[25][26] Raman reporter molecules with
olefin or alkyne moieties are being developed for tissue imaging with SERS-labeled
antibodies.[27] Raman spectroscopy has also been used as a noninvasive technique
for real-time, in situ biochemical characterization of wounds. Multivariate
analysis of Raman spectra has enabled development of a quantitative measure for
wound healing progress.[28] Spatially offset Raman spectroscopy (SORS), which is
less sensitive to surface layers than conventional Raman, can be used to discover
counterfeit drugs without opening their packaging, and to non-invasively study
biological tissue.[29] A huge reason why Raman spectroscopy is so useful in
biological applications is because its results often do not face interference from
water molecules, due to the fact that they have permanent dipole moments, and as a
result, the Raman scattering cannot be picked up on. This is a large advantage,
specifically in biological applications.[30] Raman spectroscopy also has a wide
usage for studying biominerals.[31] Lastly, Raman gas analyzers have many practical
applications, including real-time monitoring of anesthetic and respiratory gas
mixtures during surgery.

Raman spectroscopy has been used in several research projects as a means to detect
explosives from a safe distance using laser beams.[32][33][34]

Raman Spectroscopy is being further developed so it could be used in the clinical

setting. Raman4Clinic is a European organization that is working on incorporating
Raman Spectroscopy techniques in the medical field. They are currently working on
different projects, one of them being monitoring cancer using bodily fluids such as
urine and blood samples which are easily accessible. This technique would be less
stressful on the patients than constantly having to take biopsies which are not
always risk free.[35]

Art and cultural heritage

Raman spectroscopy is an efficient and non-destructive way to investigate works of
art and cultural heritage artifacts, in part because it is a non-invasive process
which can be applied in situ.[36] It can be used to analyze the corrosion products
on the surfaces of artifacts (statues, pottery, etc.), which can lend insight into
the corrosive environments experienced by the artifacts. The resulting spectra can
also be compared to the spectra of surfaces that are cleaned or intentionally
corroded, which can aid in determining the authenticity of valuable historical
artifacts.[37]

It is capable of identifying individual pigments in paintings and their degradation

products, which can provide insight into the working method of an artist in
addition to aiding in authentication of paintings.[38] It also gives information
about the original state of the painting in cases where the pigments have degraded
with age.[39] Beyond the identification of pigments, extensive Raman
microspectroscopic imaging has been shown to provide access to a plethora of trace
compounds in Early Medieval Egyptian blue, which enable to reconstruct the
individual "biography" of a colourant, including information on the type and
provenance of the raw materials, synthesis and application of the pigment, and the
ageing of the paint layer.[40]

In addition to paintings and artifacts, Raman spectroscopy can be used to

investigate the chemical composition of historical documents (such as the Book of
Kells), which can provide insight about the social and economic conditions when
they were created.[41] It also offers a noninvasive way to determine the best
method of preservation or conservation of such cultural heritage artifacts, by
providing insight into the causes behind deterioration.[42]

The IRUG (Infrared and Raman Users Group) Spectral Database[43] is a rigorously
peer-reviewed online database of IR and Raman reference spectra for cultural
heritage materials such as works of art, architecture, and archaeological
artifacts. The database is open for the general public to peruse, and includes
interactive spectra for over a hundred different types of pigments and paints.

Microspectroscopy
Main article: Raman microscope
Hyperspectral Raman imaging can provide distribution maps of chemical compounds and
material properties: Example of an unhydrated clinker remnant in a 19th-century
cement mortar (cement chemist's nomenclature: C ≙ CaO, A ≙ Al2O3, S ≙ SiO2, F ≙
Fe2O3).[7]
Raman spectroscopy offers several advantages for microscopic analysis. Since it is
a light scattering technique, specimens do not need to be fixed or sectioned. Raman
spectra can be collected from a very small volume (< 1 µm in diameter, < 10 µm in
depth); these spectra allow the identification of species present in that volume.
[44] Water does not generally interfere with Raman spectral analysis. Thus, Raman
spectroscopy is suitable for the microscopic examination of minerals, materials
such as polymers and ceramics, cells, proteins and forensic trace evidence. A Raman
microscope begins with a standard optical microscope, and adds an excitation laser,
a monochromator or polychromator, and a sensitive detector (such as a charge-
coupled device (CCD), or photomultiplier tube (PMT)). FT-Raman has also been used
with microscopes, typically in combination with near-infrared (NIR) laser
excitation. Ultraviolet microscopes and UV enhanced optics must be used when a UV
laser source is used for Raman microspectroscopy.

In direct imaging (also termed global imaging[45] or wide-field illumination), the

whole field of view is examined for light scattering integrated over a small range
of wavenumbers (Raman shifts).[46] For instance, a wavenumber characteristic for
cholesterol could be used to record the distribution of cholesterol within a cell
culture. This technique is being used for the characterization of large-scale
devices, mapping of different compounds and dynamics study. It has already been
used for the characterization of graphene layers,[47] J-aggregated dyes inside
carbon nanotubes[48] and multiple other 2D materials such as MoS2 and WSe2. Since
the excitation beam is dispersed over the whole field of view, those measurements
can be done without damaging the sample.

The most common approach is hyperspectral imaging or chemical imaging, in which

thousands of Raman spectra are acquired from all over the field of view by, for
example, raster scanning of a focused laser beam through a sample.[46] The data can
be used to generate images showing the location and amount of different components.
Having the full spectroscopic information available in every measurement spot has
the advantage that several components can be mapped at the same time, including
chemically similar and even polymorphic forms, which cannot be distinguished by
detecting only one single wavenumber. Furthermore, material properties such as
stress and strain, crystal orientation, crystallinity and incorporation of foreign
ions into crystal lattices (e.g., doping, solid solution series) can be determined
from hyperspectral maps.[7] Taking the cell culture example, a hyperspectral image
could show the distribution of cholesterol, as well as proteins, nucleic acids, and
fatty acids. Sophisticated signal- and image-processing techniques can be used to
ignore the presence of water, culture media, buffers, and other interferences.

Because a Raman microscope is a diffraction-limited system, its spatial resolution

depends on the wavelength of light, the numerical aperture of the focusing element,
and — in the case of confocal microscopy — on the diameter of the confocal
aperture. When operated in the visible to near-infrared range, a Raman microscope
can achieve lateral resolutions of approx. 1 µm down to 250 nm, depending on the
wavelength and type of objective lens (e.g., air vs. water or oil immersion
lenses). The depth resolution (if not limited by the optical penetration depth of
the sample) can range from 1–6 µm with the smallest confocal pinhole aperture to
10s of micrometers when operated without a confocal pinhole.[49][50][51][44]
Depending on the sample, the high laser power density due to microscopic focussing
can have the benefit of enhanced photobleaching of molecules emitting interfering
fluorescence. However, the laser wavelength and laser power have to be carefully
selected for each type of sample to avoid its degradation.

Applications of Raman imaging range from materials sciences to biological studies.

[44][52] For each type of sample, the measurement parameters have to be
individually optimized. For that reason, modern Raman microscopes are often
equipped with several lasers offering different wavelengths, a set of objective
lenses, and neutral density filters for tuning of the laser power reaching the
sample. Selection of the laser wavelength mainly depends on optical properties of
the sample and on the aim of the investigation.[53] For example, Raman microscopy
of biological and medical specimens is often performed using red to near-infrared
excitation (e.g., 785 nm, or 1,064 nm wavelength). Due to typically low absorbances
of biological samples in this spectral range, the risk of damaging the specimen as
well as autofluorescence emission are reduced, and high penetration depths into
tissues can be achieved.[54][55][56][57] However, the intensity of Raman scattering
at long wavelengths is low (owing to the ω4 dependence of Raman scattering
intensity), leading to long acquisition times. On the other hand, resonance Raman
imaging of single-cell algae at 532 nm (green) can specifically probe the
carotenoid distribution within a cell by a using low laser power of ~5 µW and only
100 ms acquisition time.[58]

Raman scattering, specifically tip-enhanced Raman spectroscopy, produces high

resolution hyperspectral images of single molecules,[59] atoms,[60] and DNA.[61]

Polarization dependence of Raman scattering

Raman scattering is polarization sensitive and can provide detailed information on
symmetry of Raman active modes. While conventional Raman spectroscopy identifies
chemical composition, polarization effects on Raman spectra can reveal information
on the orientation of molecules in single crystals and anisotropic materials, e.g.
strained plastic sheets, as well as the symmetry of vibrational modes.

Polarization–dependent Raman spectroscopy uses (plane) polarized laser excitation

from a polarizer. The Raman scattered light collected is passed through a second
polarizer (called the analyzer) before entering the detector. The analyzer is
oriented either parallel or perpendicular to the polarization of the laser. Spectra
acquired with the analyzer set at both perpendicular and parallel to the excitation
plane can be used to calculate the depolarization ratio. Typically a polarization
scrambler is placed between the analyzer and detector also. It is convenient in
polarized Raman spectroscopy to describe the propagation and polarization
directions using Porto's notation,[62] described by and named after Brazilian
physicist Sergio Pereira da Silva Porto.

For isotropic solutions, the Raman scattering from each mode either retains the
polarization of the laser or becomes partly or fully depolarized. If the
vibrational mode involved in the Raman scattering process is totally symmetric then
the polarization of the Raman scattering will be the same as that of the incoming
laser beam. In the case that the vibrational mode is not totally symmetric then the
polarization will be lost (scrambled) partially or totally, which is referred to as
depolarization. Hence polarized Raman spectroscopy can provide detailed information
as to the symmetry labels of vibrational modes.

In the solid state, polarized Raman spectroscopy can be useful in the study of
oriented samples such as single crystals. The polarizability of a vibrational mode
is not equal along and across the bond. Therefore the intensity of the Raman
scattering will be different when the laser's polarization is along and orthogonal
to a particular bond axis. This effect can provide information on the orientation
of molecules with a single crystal or material. The spectral information arising
from this analysis is often used to understand macro-molecular orientation in
crystal lattices, liquid crystals or polymer samples.[63]

Characterization of the symmetry of a vibrational mode

The polarization technique is useful in understanding the connections between
molecular symmetry, Raman activity, and peaks in the corresponding Raman spectra.
[64] Polarized light in one direction only gives access to some Raman–active modes,
but rotating the polarization gives access to other modes. Each mode is separated
according to its symmetry.[65]

The symmetry of a vibrational mode is deduced from the depolarization ratio ρ,

which is the ratio of the Raman scattering with polarization orthogonal to the
incident laser and the Raman scattering with the same polarization as the incident
laser: {\displaystyle \rho ={\frac {I_{r}}{I_{u}}}}{\displaystyle \rho ={\frac
{I_{r}}{I_{u}}}} Here {\displaystyle I_{r}}I_r is the intensity of Raman scattering
when the analyzer is rotated 90 degrees with respect to the incident light's
polarization axis, and {\displaystyle I_{u}}I_{u} the intensity of Raman scattering
when the analyzer is aligned with the polarization of the incident laser.[66] When
polarized light interacts with a molecule, it distorts the molecule which induces
an equal and opposite effect in the plane-wave, causing it to be rotated by the
difference between the orientation of the molecule and the angle of polarization of
the light wave. If ρ ≥ {\displaystyle {\frac {3}{4}}}{\frac {3}{4}}, then the
vibrations at that frequency are depolarized; meaning they are not totally
symmetric.[67][66]

Variants
At least 25 variations of Raman spectroscopy have been developed.[8] The usual
purpose is to enhance the sensitivity (e.g., surface-enhanced Raman), to improve
the spatial resolution (Raman microscopy), or to acquire very specific information
(resonance Raman).

Spontaneous (or far-field) Raman spectroscopy

Correlative Raman imaging: Comparison of topographical (AFM, top) and Raman images
of GaSe. Scale bar is 5 μm.[68]
Terms such as spontaneous Raman spectroscopy or normal Raman spectroscopy summarize
Raman spectroscopy techniques based on Raman scattering by using normal far-field
optics as described above. Variants of normal Raman spectroscopy exist with respect
to excitation-detection geometries, combination with other techniques, use of
special (polarizing) optics and specific choice of excitation wavelengths for
resonance enhancement.

Correlative Raman imaging – Raman microscopy can be combined with complementary

imaging methods, such as atomic force microscopy (Raman-AFM) and scanning electron
microscopy (Raman-SEM) to compare Raman distribution maps with (or overlay them
onto) topographical or morphological images, and to correlate Raman spectra with
complementary physical or chemical information (e.g., gained by SEM-EDX).
Resonance Raman spectroscopy – The excitation wavelength is matched to an
electronic transition of the molecule or crystal, so that vibrational modes
associated with the excited electronic state are greatly enhanced. This is useful
for studying large molecules such as polypeptides, which might show hundreds of
bands in "conventional" Raman spectra. It is also useful for associating normal
modes with their observed frequency shifts.[69]
Angle-resolved Raman spectroscopy – Not only are standard Raman results recorded
but also the angle with respect to the incident laser. If the orientation of the
sample is known then detailed information about the phonon dispersion relation can
also be gleaned from a single test.[70]
Optical tweezers Raman spectroscopy (OTRS) – Used to study individual particles,
and even biochemical processes in single cells trapped by optical tweezers.[71][72]
[73]
Spatially offset Raman spectroscopy (SORS) – The Raman scattering beneath an
obscuring surface is retrieved from a scaled subtraction of two spectra taken at
two spatially offset points.
Raman optical activity (ROA) – Measures vibrational optical activity by means of a
small difference in the intensity of Raman scattering from chiral molecules in
right- and left-circularly polarized incident light or, equivalently, a small
circularly polarized component in the scattered light.[74]
Transmission Raman – Allows probing of a significant bulk of a turbid material,
such as powders, capsules, living tissue, etc. It was largely ignored following
investigations in the late 1960s (Schrader and Bergmann, 1967)[75] but was
rediscovered in 2006 as a means of rapid assay of pharmaceutical dosage forms.[76]
There are medical diagnostic applications particularly in the detection of cancer.
[34][77][78]
Micro-cavity substrates – A method that improves the detection limit of
conventional Raman spectra using micro-Raman in a micro-cavity coated with
reflective Au or Ag. The micro-cavity has a radius of several micrometers and
enhances the entire Raman signal by providing multiple excitations of the sample
and couples the forward-scattered Raman photons toward the collection optics in the
back-scattered Raman geometry.[79]
Stand-off remote Raman. – In standoff Raman, the sample is measured at a distance
from the Raman spectrometer, usually by using a telescope for light collection.
Remote Raman spectroscopy was proposed in the 1960s[80] and initially developed for
the measurement of atmospheric gases.[81] The technique was extended In 1992 by
Angel et al. for standoff Raman detection of hazardous inorganic and organic
compounds.[82]
X-ray Raman scattering – Measures electronic transitions rather than vibrations.
[83]
Enhanced (or near-field) Raman spectroscopy
Enhancement of Raman scattering is achieved by local electric-field enhancement by
optical near-field effects (e.g. localized surface plasmons).

Surface-enhanced Raman spectroscopy (SERS) – Normally done in a silver or gold

colloid or a substrate containing silver or gold. Surface plasmons of silver and
gold are excited by the laser, resulting in an increase in the electric fields
surrounding the metal. Given that Raman intensities are proportional to the
electric field, there is large increase in the measured signal (by up to 1011).
This effect was originally observed by Martin Fleischmann but the prevailing
explanation was proposed by Van Duyne in 1977.[84] A comprehensive theory of the
effect was given by Lombardi and Birke.[85]
Surface-enhanced resonance Raman spectroscopy (SERRS) – A combination of SERS and
resonance Raman spectroscopy that uses proximity to a surface to increase Raman
intensity, and excitation wavelength matched to the maximum absorbance of the
molecule being analysed.
Tip-enhanced Raman spectroscopy (TERS) – Uses a metallic (usually silver-/gold-
coated AFM or STM) tip to enhance the Raman signals of molecules situated in its
vicinity. The spatial resolution is approximately the size of the tip apex (20–30
nm). TERS has been shown to have sensitivity down to the single molecule level [86]
[87][88][89] and holds some promise for bioanalysis applications [90] and DNA
sequencing.[61] TERS was used to image the vibrational normal modes of single
molecules.[91]
Surface plasmon polariton enhanced Raman scattering (SPPERS) – This approach
exploits apertureless metallic conical tips for near field excitation of molecules.
This technique differs from the TERS approach due to its inherent capability of
suppressing the background field. In fact, when an appropriate laser source
impinges on the base of the cone, a TM0 mode[92] (polaritonic mode) can be locally
created, namely far away from the excitation spot (apex of the tip). The mode can
propagate along the tip without producing any radiation field up to the tip apex
where it interacts with the molecule. In this way, the focal plane is separated
from the excitation plane by a distance given by the tip length, and no background
plays any role in the Raman excitation of the molecule.[93][94][95][96]
Non-linear Raman spectroscopy
Raman signal enhancements are achieved through non-linear optical effects,
typically realized by mixing two or more wavelengths emitted by spatially and
temporally synchronized pulsed lasers.
Hyper Raman – A non-linear effect in which the vibrational modes interact with the
second harmonic of the excitation beam. This requires very high power, but allows
the observation of vibrational modes that are normally "silent". It frequently
relies on SERS-type enhancement to boost the sensitivity.[97]
Stimulated Raman spectroscopy (SRS) – A pump-probe technique, where a spatially
coincident, two color pulse (with polarization either parallel or perpendicular)
transfers the population from ground to a rovibrationally excited state. If the
difference in energy corresponds to an allowed Raman transition, scattered light
will correspond to loss or gain in the pump beam.
Inverse Raman spectroscopy – A synonym for stimulated Raman loss spectroscopy.
Coherent anti-Stokes Raman spectroscopy (CARS) – Two laser beams are used to
generate a coherent anti-Stokes frequency beam, which can be enhanced by resonance.
Morphologically-Directed Raman spectroscopy
Morphologically Directed Raman Spectroscopy (MDRS) combines automated particle
imaging and Raman microspectroscopy into a singular integrated platform in order to
provide particle size, shape, and chemical identification.[98][99][100] Automated
particle imaging determines the particle size and shape distributions of components
within a blended sample from images of individual particles.[99][100] The
information gathered from automated particle imaging is then utilized to direct the
Raman spectroscopic analysis.[98] The Raman spectroscopic analytical process is
performed on a randomly-selected subset of the particles, allowing chemical
identification of the sample’s multiple components.[98] Tens of thousands of
particles can be imaged in a matter of minutes using the MDRS method, making the
process ideal for forensic analysis and investigating counterfeit pharmaceuticals
and subsequent adjudications.[99][100]

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