Spectroscopy

Spectroscopy /spɛkˈtrɒskəpi/ is the study of the interaction between matter and electromagnetic radiation.[1][2] Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, by a prism. Later the concept was expanded greatly to include any interaction with radiative energy as a function of its wavelength or frequency, predominantly in the electromagnetic spectrum, though matter waves and acoustic waves can also be considered forms of radiative energy; recently, with tremendous difficulty, even gravitational waves have been associated with a spectral signature in the context of LIGO and laser interferometry. Spectroscopic data are often represented by an emission spectrum, a plot of the response of interest as a function of wavelength or frequency.

Spectroscopy, primarily in the electromagnetic spectrum, is a fundamental exploratory tool in the fields of physics, chemistry, and astronomy, allowing the composition, physical structure and electronic structure of matter to be investigated at atomic scale, molecular scale, macro scale, and over astronomical distances. Important applications arise from biomedical spectroscopy in the areas of tissue analysis and medical imaging.

Light dispersion of a mercury-vapor lamp with a flint glass prism IPNr°0125
Analysis of white light by dispersing it with a prism is an example of spectroscopy.

Introduction

Spectroscopy and spectrography are terms used to refer to the measurement of radiation intensity as a function of wavelength and are often used to describe experimental spectroscopic methods. Spectral measurement devices are referred to as spectrometers, spectrophotometers, spectrographs or spectral analyzers.

Daily observations of color can be related to spectroscopy. Neon lighting is a direct application of atomic spectroscopy. Neon and other noble gases have characteristic emission frequencies (colors). Neon lamps use collision of electrons with the gas to excite these emissions. Inks, dyes and paints include chemical compounds selected for their spectral characteristics in order to generate specific colors and hues. A commonly encountered molecular spectrum is that of nitrogen dioxide. Gaseous nitrogen dioxide has a characteristic red absorption feature, and this gives air polluted with nitrogen dioxide a reddish-brown color. Rayleigh scattering is a spectroscopic scattering phenomenon that accounts for the color of the sky.

Spectroscopic studies were central to the development of quantum mechanics and included Max Planck's explanation of blackbody radiation, Albert Einstein's explanation of the photoelectric effect and Niels Bohr's explanation of atomic structure and spectra. Spectroscopy is used in physical and analytical chemistry because atoms and molecules have unique spectra. As a result, these spectra can be used to detect, identify and quantify information about the atoms and molecules. Spectroscopy is also used in astronomy and remote sensing on Earth. Most research telescopes have spectrographs. The measured spectra are used to determine the chemical composition and physical properties of astronomical objects (such as their temperature and velocity).

Theory

One of the central concepts in spectroscopy is a resonance and its corresponding resonant frequency. Resonances were first characterized in mechanical systems such as pendulums. Mechanical systems that vibrate or oscillate will experience large amplitude oscillations when they are driven at their resonant frequency. A plot of amplitude vs. excitation frequency will have a peak centered at the resonance frequency. This plot is one type of spectrum, with the peak often referred to as a spectral line, and most spectral lines have a similar appearance.

In quantum mechanical systems, the analogous resonance is a coupling of two quantum mechanical stationary states of one system, such as an atom, via an oscillatory source of energy such as a photon. The coupling of the two states is strongest when the energy of the source matches the energy difference between the two states. The energy of a photon is related to its frequency by where is Planck's constant, and so a spectrum of the system response vs. photon frequency will peak at the resonant frequency or energy. Particles such as electrons and neutrons have a comparable relationship, the de Broglie relations, between their kinetic energy and their wavelength and frequency and therefore can also excite resonant interactions.

Spectra of atoms and molecules often consist of a series of spectral lines, each one representing a resonance between two different quantum states. The explanation of these series, and the spectral patterns associated with them, were one of the experimental enigmas that drove the development and acceptance of quantum mechanics. The hydrogen spectral series in particular was first successfully explained by the Rutherford-Bohr quantum model of the hydrogen atom. In some cases spectral lines are well separated and distinguishable, but spectral lines can also overlap and appear to be a single transition if the density of energy states is high enough. Named series of lines include the principal, sharp, diffuse and fundamental series.

Classification of methods

A Taste of ESPRESSO
A huge diffraction grating at the heart of the ultra-precise ESPRESSO spectrograph.[3]

Spectroscopy is a sufficiently broad field that many sub-disciplines exist, each with numerous implementations of specific spectroscopic techniques. The various implementations and techniques can be classified in several ways.

Type of radiative energy

The types of spectroscopy are distinguished by the type of radiative energy involved in the interaction. In many applications, the spectrum is determined by measuring changes in the intensity or frequency of this energy. The types of radiative energy studied include:

Nature of the interaction

The types of spectroscopy also can be distinguished by the nature of the interaction between the energy and the material. These interactions include:[1]

  • Absorption spectroscopy: Absorption occurs when energy from the radiative source is absorbed by the material. Absorption is often determined by measuring the fraction of energy transmitted through the material, with absorption decreasing the transmitted portion.
  • Emission spectroscopy: Emission indicates that radiative energy is released by the material. A material's blackbody spectrum is a spontaneous emission spectrum determined by its temperature. This feature can be measured in the infrared by instruments such as the atmospheric emitted radiance interferometer.[4] Emission can also be induced by other sources of energy such as flames or sparks or electromagnetic radiation in the case of fluorescence.
  • Elastic scattering and reflection spectroscopy determine how incident radiation is reflected or scattered by a material. Crystallography employs the scattering of high energy radiation, such as x-rays and electrons, to examine the arrangement of atoms in proteins and solid crystals.
  • Impedance spectroscopy: Impedance is the ability of a medium to impede or slow the transmittance of energy. For optical applications, this is characterized by the index of refraction.
  • Inelastic scattering phenomena involve an exchange of energy between the radiation and the matter that shifts the wavelength of the scattered radiation. These include Raman and Compton scattering.
  • Coherent or resonance spectroscopy are techniques where the radiative energy couples two quantum states of the material in a coherent interaction that is sustained by the radiating field. The coherence can be disrupted by other interactions, such as particle collisions and energy transfer, and so often require high intensity radiation to be sustained. Nuclear magnetic resonance (NMR) spectroscopy is a widely used resonance method, and ultrafast laser spectroscopy is also possible in the infrared and visible spectral regions.

Type of material

Spectroscopic studies are designed so that the radiant energy interacts with specific types of matter.

Atoms

Atomic spectroscopy was the first application of spectroscopy developed. Atomic absorption spectroscopy and atomic emission spectroscopy involve visible and ultraviolet light. These absorptions and emissions, often referred to as atomic spectral lines, are due to electronic transitions of outer shell electrons as they rise and fall from one electron orbit to another. Atoms also have distinct x-ray spectra that are attributable to the excitation of inner shell electrons to excited states.

Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the identification and quantitation of a sample's elemental composition. After inventing the spectroscope, Robert Bunsen and Gustav Kirchhoff discovered new elements by observing their emission spectra. Atomic absorption lines are observed in the solar spectrum and referred to as Fraunhofer lines after their discoverer. A comprehensive explanation of the hydrogen spectrum was an early success of quantum mechanics and explained the Lamb shift observed in the hydrogen spectrum, which further led to the development of quantum electrodynamics.

Modern implementations of atomic spectroscopy for studying visible and ultraviolet transitions include flame emission spectroscopy, inductively coupled plasma atomic emission spectroscopy, glow discharge spectroscopy, microwave induced plasma spectroscopy, and spark or arc emission spectroscopy. Techniques for studying x-ray spectra include X-ray spectroscopy and X-ray fluorescence.

Molecules

The combination of atoms into molecules leads to the creation of unique types of energetic states and therefore unique spectra of the transitions between these states. Molecular spectra can be obtained due to electron spin states (electron paramagnetic resonance), molecular rotations, molecular vibration, and electronic states. Rotations are collective motions of the atomic nuclei and typically lead to spectra in the microwave and millimeter-wave spectral regions. Rotational spectroscopy and microwave spectroscopy are synonymous. Vibrations are relative motions of the atomic nuclei and are studied by both infrared and Raman spectroscopy. Electronic excitations are studied using visible and ultraviolet spectroscopy as well as fluorescence spectroscopy.

Studies in molecular spectroscopy led to the development of the first maser and contributed to the subsequent development of the laser.

Crystals and extended materials

The combination of atoms or molecules into crystals or other extended forms leads to the creation of additional energetic states. These states are numerous and therefore have a high density of states. This high density often makes the spectra weaker and less distinct, i.e., broader. For instance, blackbody radiation is due to the thermal motions of atoms and molecules within a material. Acoustic and mechanical responses are due to collective motions as well. Pure crystals, though, can have distinct spectral transitions, and the crystal arrangement also has an effect on the observed molecular spectra. The regular lattice structure of crystals also scatters x-rays, electrons or neutrons allowing for crystallographic studies.

Nuclei

Nuclei also have distinct energy states that are widely separated and lead to gamma ray spectra. Distinct nuclear spin states can have their energy separated by a magnetic field, and this allows for nuclear magnetic resonance spectroscopy.

Other types

Other types of spectroscopy are distinguished by specific applications or implementations:

Applications

UVES on UT2-KUEYEN
UVES is a high-resolution spectrograph on the Very Large Telescope.[12]
  • Cure monitoring of composites using optical fibers.
  • Estimate weathered wood exposure times using near infrared spectroscopy.[13]
  • Measurement of different compounds in food samples by absorption spectroscopy both in visible and infrared spectrum.
  • Measurement of toxic compounds in blood samples
  • Non-destructive elemental analysis by X-ray fluorescence.
  • Electronic structure research with various spectroscopes.

History

The history of spectroscopy began with Isaac Newton's optics experiments (1666–1672). Newton applied the word "spectrum" to describe the rainbow of colors that combine to form white light and that are revealed when the white light is passed through a prism. During the early 1800s, Joseph von Fraunhofer made experimental advances with dispersive spectrometers that enabled spectroscopy to become a more precise and quantitative scientific technique. Since then, spectroscopy has played and continues to play a significant role in chemistry, physics, and astronomy.

  • "In 1672, in the first paper that he submitted to the Royal Society, Isaac Newton described an experiment in which he permitted sunlight to pass through a small hole and then through a prism. Newton found that sunlight, which looks white to us, is actually made up of a mixture of all the colors of the rainbow."[14]
  • "In 1802, William Hyde Wollaston built an improved spectrometer that included a lens to focus the Sun’s spectrum on a screen. Upon use, Wollaston realized that the colors were not spread uniformly, but instead had missing patches of colors, which appeared as dark bands in the spectrum. Later, in 1815, German physicist Joseph Fraunhofer also examined the solar spectrum, and found about 600 such dark lines (missing colors), which are now known as Fraunhofer lines, or Absorption lines."[14]

See also

Notes

  1. ^ a b Crouch, Stanley; Skoog, Douglas A. (2007). Principles of instrumental analysis. Australia: Thomson Brooks/Cole. ISBN 978-0-495-01201-6.
  2. ^ Herrmann, R.; C. Onkelinx (1986). "Quantities and units in clinical chemistry: Nebulizer and flame properties in flame emission and absorption spectrometry (Recommendations 1986)". Pure and Applied Chemistry. 58 (12): 1737–1742. doi:10.1351/pac198658121737.
  3. ^ "A Taste of ESPRESSO". Retrieved 15 September 2015.
  4. ^ Mariani, Z.; Strong, K.; Wolff, M.; Rowe, P.; Walden, V.; Fogal, P. F.; Duck, T.; Lesins, G.; Turner, D. S.; Cox, C.; Eloranta, E.; Drummond, J. R.; Roy, C.; Turner, D. D.; Hudak, D.; Lindenmaier, I. A. (2012). "Infrared measurements in the Arctic using two Atmospheric Emitted Radiance Interferometers". Atmos. Meas. Tech. 5 (2): 329–344. Bibcode:2012AMT.....5..329M. doi:10.5194/amt-5-329-2012.
  5. ^ Evans, C. L.; Xie, X. S. (2008). "Coherent Anti-Stokes Raman Scattering Microscopy: Chemical Imaging for Biology and Medicine". Annual Review of Analytical Chemistry. 1: 883–909. Bibcode:2008ARAC....1..883E. doi:10.1146/annurev.anchem.1.031207.112754. PMID 20636101.
  6. ^ W. Demtröder, Laser Spectroscopy, 3rd Ed. (Springer, 2003).
  7. ^ Brian Orr; J. G. Haub; Y. He; R. T. White (2016). "Spectroscopic Applications of Pulsed Tunable Optical Parametric Oscillators". In F. J. Duarte (ed.). Tunable Laser Applications (3rd ed.). Boca Raton: CRC Press. pp. 17–142. ISBN 978-1-4822-6106-6.
  8. ^ Murray, Kermit K.; Boyd, Robert K.; Eberlin, Marcos N.; Langley, G. John; Li, Liang; Naito, Yasuhide (2013). "Definitions of terms relating to mass spectrometry (IUPAC Recommendations 2013)". Pure and Applied Chemistry. 85 (7): 1. doi:10.1351/PAC-REC-06-04-06. ISSN 0033-4545.
  9. ^ N. A. Sinitsyn; Y. V. Pershin (2016). "The theory of spin noise spectroscopy: a review". Reports on Progress in Physics. 79 (10): 106501. arXiv:1603.06858. Bibcode:2016RPPh...79j6501S. doi:10.1088/0034-4885/79/10/106501. PMID 27615689.
  10. ^ Solli, D. R.; Chou, J.; Jalali, B. (2008). "Amplified wavelength–time transformation for real-time spectroscopy". Nature Photonics. 2 (1): 48–51. Bibcode:2008NaPho...2...48S. doi:10.1038/nphoton.2007.253.
  11. ^ Chou, Jason; Solli, Daniel R.; Jalali, Bahram (2008). "Real-time spectroscopy with subgigahertz resolution using amplified dispersive Fourier transformation". Applied Physics Letters. 92 (11): 111102. arXiv:0803.1654. Bibcode:2008ApPhL..92k1102C. doi:10.1063/1.2896652.
  12. ^ "Media advisory: Press Conference to Announce Major Result from Brazilian Astronomers". ESO Announcement. Retrieved 21 August 2013.
  13. ^ Wang, Xiping; Wacker, James P. (2006). "Using NIR Spectroscopy to Predict Weathered Wood Exposure Times" (PDF). WTCE 2006 – 9th World Conference on Timber Engineering.
  14. ^ a b Andrew Fraknoi; David Morrison (October 13, 2016). "OpenStax Astronomy".

References

External links

Absorption spectroscopy

Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.

Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet-visible spectroscopy are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing.

There are a wide range of experimental approaches for measuring absorption spectra. The most common arrangement is to direct a generated beam of radiation at a sample and detect the intensity of the radiation that passes through it. The transmitted energy can be used to calculate the absorption. The source, sample arrangement and detection technique vary significantly depending on the frequency range and the purpose of the experiment.

Astronomical spectroscopy

Astronomical spectroscopy is the study of astronomy using the techniques of spectroscopy to measure the spectrum of electromagnetic radiation, including visible light and radio, which radiates from stars and other celestial objects. A stellar spectrum can reveal many properties of stars, such as their chemical composition, temperature, density, mass, distance, luminosity, and relative motion using Doppler shift measurements. Spectroscopy is also used to study the physical properties of many other types of celestial objects such as planets, nebulae, galaxies, and active galactic nuclei.

Doppler spectroscopy

Doppler spectroscopy (also known as the radial-velocity method, or colloquially, the wobble method) is an indirect method for finding extrasolar planets and brown dwarfs from radial-velocity measurements via observation of Doppler shifts in the spectrum of the planet's parent star.

669 extrasolar planets (about 29.6% of the total) were discovered using Doppler spectroscopy, as of April 2016.

Electron paramagnetic resonance

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

is a method for studying materials with unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but it is electron spins that are excited instead of the spins of atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes or organic radicals.

EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford.

Emission spectrum

The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to an atom or molecule making a transition from a high energy state to a lower energy state. The photon energy of the emitted photon is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify the elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.

Energy-dispersive X-ray spectroscopy

Energy-dispersive X-ray spectroscopy (EDS, EDX, EDXS or XEDS), sometimes called energy dispersive X-ray analysis (EDXA) or energy dispersive X-ray microanalysis (EDXMA), is an analytical technique used for the elemental analysis or chemical characterization of a sample. It relies on an interaction of some source of X-ray excitation and a sample. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing a unique set of peaks on its electromagnetic emission spectrum (which is the main principle of spectroscopy).

To stimulate the emission of characteristic X-rays from a specimen, a high-energy beam of charged particles such as electrons or protons (see PIXE), or a beam of X-rays, is focused into the sample being studied. At rest, an atom within the sample contains ground state (or unexcited) electrons in discrete energy levels or electron shells bound to the nucleus. The incident beam may excite an electron in an inner shell, ejecting it from the shell while creating an electron hole where the electron was. An electron from an outer, higher-energy shell then fills the hole, and the difference in energy between the higher-energy shell and the lower energy shell may be released in the form of an X-ray. The number and energy of the X-rays emitted from a specimen can be measured by an energy-dispersive spectrometer. As the energies of the X-rays are characteristic of the difference in energy between the two shells and of the atomic structure of the emitting element, EDS allows the elemental composition of the specimen to be measured.

Femtochemistry

Femtochemistry is the area of physical chemistry that studies chemical reactions on extremely short timescales (approximately 10−15 seconds or one femtosecond, hence the name) in order to study the very act of atoms within molecules (reactants) rearranging themselves to form new molecules (products). In 1999, Ahmed Hassan Zewail received the Nobel Prize in Chemistry for his pioneering work in this field showing that it is possible to see how atoms in a molecule move during a chemical reaction with flashes of laser light.Application of femtochemistry in biological studies has also helped to elucidate the conformational dynamics of stem-loop RNA structures.Many publications have discussed the possibility of controlling chemical reactions by this method, but this remains controversial. The steps in some reactions occur in the femtosecond timescale and sometimes in attosecond timescales, and will sometimes form intermediate products. These reaction intermediates cannot always be deduced from observing the start and end products.

Fluorescence spectroscopy

Fluorescence spectroscopy (also known as fluorimetry or spectrofluorometry) is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.

Devices that measure fluorescence are called fluorometers.

Fourier-transform infrared spectroscopy

Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simultaneously collects high-spectral-resolution data over a wide spectral range. This confers a significant advantage over a dispersive spectrometer, which measures intensity over a narrow range of wavelengths at a time.

The term Fourier-transform infrared spectroscopy originates from the fact that a Fourier transform (a mathematical process) is required to convert the raw data into the actual spectrum. For other uses of this kind of technique, see Fourier-transform spectroscopy.

Infrared spectroscopy

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) involves the interaction of infrared radiation with matter. It covers a range of techniques, mostly based on absorption spectroscopy. As with all spectroscopic techniques, it can be used to identify and study chemicals. Samples may be solid, liquid, or gas. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer (or spectrophotometer) to produce an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance (or transmittance) on the vertical axis vs. frequency or wavelength on the horizontal axis. Typical units of frequency used in IR spectra are reciprocal centimeters (sometimes called wave numbers), with the symbol cm−1. Units of IR wavelength are commonly given in micrometers (formerly called "microns"), symbol μm, which are related to wave numbers in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher-energy near-IR, approximately 14000–4000 cm−1 (0.7–2.5 μm wavelength) can excite overtone or harmonic vibrations. The mid-infrared, approximately 4000–400 cm−1 (2.5–25 μm) may be used to study the fundamental vibrations and associated rotational-vibrational structure. The far-infrared, approximately 400–10 cm−1 (25–1000 μm), lying adjacent to the microwave region, has low energy and may be used for rotational spectroscopy. The names and classifications of these subregions are conventions, and are only loosely based on the relative molecular or electromagnetic properties.

Mössbauer spectroscopy

Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (also Moessbauer, German: "Mößbauer") in 1958, consists in the nearly recoil-free, resonant absorption and emission of gamma rays in solids.

Like nuclear magnetic resonance spectroscopy, Mössbauer spectroscopy probes tiny changes in the energy levels of an atomic nucleus in response to its environment. Typically, three types of nuclear interactions may be observed: isomer shift, also called chemical shift in the older literature; quadrupole splitting; and magnetic hyperfine splitting (see also the Zeeman effect). Due to the high energy and extremely narrow line widths of gamma rays, Mössbauer spectroscopy is a very sensitive technique in terms of energy (and hence frequency) resolution, capable of detecting changes in just a few parts per 1011.

Near-infrared spectroscopy

Near-infrared spectroscopy (NIRS) is a spectroscopic method that uses the near-infrared region of the electromagnetic spectrum (from 780 nm to 2500 nm). Typical applications include medical and physiological diagnostics and research including blood sugar, pulse oximetry, functional neuroimaging, sports medicine, elite sports training, ergonomics, rehabilitation, neonatal research, brain computer interface, urology (bladder contraction), and neurology (neurovascular coupling). There are also applications in other areas as well such as pharmaceutical, food and agrochemical quality control, atmospheric chemistry, combustion research and astronomy.

Nuclear magnetic resonance

Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong static magnetic field are perturbed by a weak oscillating magnetic field (in the near field and therefore not involving electromagnetic waves) and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near resonance, when the oscillation frequency matches the intrinsic frequency of the nuclei, which depends on the strength of the static magnetic field, the chemical environment, and the magnetic properties of the isotope involved; in practical applications with static magnetic fields up to ca. 20 tesla, the frequency is similar to VHF and UHF television broadcasts (60–1000 MHz). NMR results from specific magnetic properties of certain atomic nuclei. Nuclear magnetic resonance spectroscopy is widely used to determine the structure of organic molecules in solution and study molecular physics, crystals as well as non-crystalline materials. NMR is also routinely used in advanced medical imaging techniques, such as in magnetic resonance imaging (MRI).

All isotopes that contain an odd number of protons and/or neutrons (see Isotope) have an intrinsic nuclear magnetic moment and angular momentum, in other words a nonzero nuclear spin, while all nuclides with even numbers of both have a total spin of zero. The most commonly used nuclei are 1H and 13C, although isotopes of many other elements can be studied by high-field NMR spectroscopy as well.

A key feature of NMR is that the resonance frequency of a particular simple substance is usually directly proportional to the strength of the applied magnetic field. It is this feature that is exploited in imaging techniques; if a sample is placed in a non-uniform magnetic field then the resonance frequencies of the sample's nuclei depend on where in the field they are located. Since the resolution of the imaging technique depends on the magnitude of the magnetic field gradient, many efforts are made to develop increased gradient field strength.

The principle of NMR usually involves three sequential steps:

The alignment (polarization) of the magnetic nuclear spins in an applied, constant magnetic field B0.

The perturbation of this alignment of the nuclear spins by a weak oscillating magnetic field, usually referred to as a radio-frequency (RF) pulse. The oscillation frequency required for significant perturbation is dependent upon the static magnetic field (B0) and the nuclei of observation.

The detection of the NMR signal during or after the RF pulse, due to the voltage induced in a detection coil by precession of the nuclear spins around B0. After an RF pulse, precession usually occurs with the nuclei's intrinsic Larmor frequency and, in itself, does not involve transitions between spin states or energy levels.The two magnetic fields are usually chosen to be perpendicular to each other as this maximizes the NMR signal strength. The frequencies of the time-signal response by the total magnetization (M) of the nuclear spins are analyzed in NMR spectroscopy and magnetic resonance imaging. Both use applied magnetic fields (B0) of great strength, often produced by large currents in superconducting coils, in order to achieve dispersion of response frequencies and of very high homogeneity and stability in order to deliver spectral resolution, the details of which are described by chemical shifts, the Zeeman effect, and Knight shifts (in metals). The information provided by NMR can also be increased using hyperpolarization, and/or using two-dimensional, three-dimensional and higher-dimensional techniques.

NMR phenomena are also utilized in low-field NMR, NMR spectroscopy and MRI in the Earth's magnetic field (referred to as Earth's field NMR), and in several types of magnetometers.

Nuclear magnetic resonance spectroscopy

Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic field and the NMR signal is produced by excitation of the nuclei sample with radio waves into nuclear magnetic resonance, which is detected with sensitive radio receivers. The intramolecular magnetic field around an atom in a molecule changes the resonance frequency, thus giving access to details of the electronic structure of a molecule and its individual functional groups. As the fields are unique or highly characteristic to individual compounds, in modern organic chemistry practice, NMR spectroscopy is the definitive method to identify monomolecular organic compounds. Similarly, biochemists use NMR to identify proteins and other complex molecules. Besides identification, NMR spectroscopy provides detailed information about the structure, dynamics, reaction state, and chemical environment of molecules. The most common types of NMR are proton and carbon-13 NMR spectroscopy, but it is applicable to any kind of sample that contains nuclei possessing spin.

NMR spectra are unique, well-resolved, analytically tractable and often highly predictable for small molecules. Different functional groups are obviously distinguishable, and identical functional groups with differing neighboring substituents still give distinguishable signals. NMR has largely replaced traditional wet chemistry tests such as color reagents or typical chromatography for identification. A disadvantage is that a relatively large amount, 2–50 mg, of a purified substance is required, although it may be recovered through a workup. Preferably, the sample should be dissolved in a solvent, because NMR analysis of solids requires a dedicated magic angle spinning machine and may not give equally well-resolved spectra. The timescale of NMR is relatively long, and thus it is not suitable for observing fast phenomena, producing only an averaged spectrum. Although large amounts of impurities do show on an NMR spectrum, better methods exist for detecting impurities, as NMR is inherently not very sensitive - though at higher frequencies, sensitivity is higher.

Correlation spectroscopy is a development of ordinary NMR. In two-dimensional NMR, the emission is centered around a single frequency, and correlated resonances are observed. This allows identifying the neighboring substituents of the observed functional group, allowing unambiguous identification of the resonances. There are also more complex 3D and 4D methods and a variety of methods designed to suppress or amplify particular types of resonances. In nuclear Overhauser effect (NOE) spectroscopy, the relaxation of the resonances is observed. As NOE depends on the proximity of the nuclei, quantifying the NOE for each nucleus allows for construction of a three-dimensional model of the molecule.

NMR spectrometers are relatively expensive; universities usually have them, but they are less common in private companies. Modern NMR spectrometers have a very strong, large and expensive liquid helium-cooled superconducting magnet, because resolution directly depends on magnetic field strength. Less expensive machines using permanent magnets and lower resolution are also available, which still give sufficient performance for certain application such as reaction monitoring and quick checking of samples. There are even benchtop nuclear magnetic resonance spectrometers. NMR can be observed in magnetic fields less than a millitesla. Low-resolution NMR produces broader peaks which can easily overlap one another causing issues in resolving complex structures. The use of higher strength magnetic fields result in clear resolution of the peaks and is the standard in industry.

Raman spectroscopy

Raman spectroscopy (); named after Indian physicist Sir C. V. Raman) is a spectroscopic technique used to observe vibrational, rotational, and other low-frequency modes in a system. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.

It relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range. 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 yields similar, but 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, and as a result the main difficulty of Raman spectroscopy is separating the weak inelastically scattered light from the intense Rayleigh scattered laser light. 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 and spectrographs either axial transmissive (AT), Czerny–Turner (CT) monochromator, or FT (Fourier transform spectroscopy based), and CCD detectors.

The advanced types of Raman spectroscopy include surface-enhanced Raman, resonance Raman, tip-enhanced Raman, polarized Raman, stimulated Raman (analogous to stimulated emission), transmission Raman, spatially offset Raman, and hyper Raman.

Spectral line

A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected "fingerprints" of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.

Ultraviolet–visible spectroscopy

Ultraviolet–visible spectroscopy or ultraviolet–visible spectrophotometry (UV–Vis or UV/Vis) refers to absorption spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full, adjacent visible spectral regions. This means it uses light in the visible and adjacent ranges. The absorption or reflectance in the visible range directly affects the perceived color of the chemicals involved. In this region of the electromagnetic spectrum, atoms and molecules undergo electronic transitions. Absorption spectroscopy is complementary to fluorescence spectroscopy, in that fluorescence deals with transitions from the excited state to the ground state, while absorption measures transitions from the ground state to the excited state.

Wavenumber

In the physical sciences, the wavenumber (also wave number or repetency) is the spatial frequency of a wave, measured in cycles per unit distance or radians per unit distance. Whereas temporal frequency can be thought of as the number of waves per unit time, wavenumber is the number of waves per unit distance.

In multidimensional systems, the wavenumber is the magnitude of the wave vector. The space of wave vectors is called reciprocal space. Wave numbers and wave vectors play an essential role in optics and the physics of wave scattering, such as X-ray diffraction, neutron diffraction, and elementary particle physics. For quantum mechanical waves, the wavenumber multiplied by Planck's constant is the canonical momentum.

Wavenumber can be used to specify quantities other than spatial frequency. In optical spectroscopy, it is often used as a unit of temporal frequency assuming a certain speed of light.

X-ray spectroscopy

X-ray spectroscopy is a general term for several spectroscopic techniques for characterization of materials by using x-ray excitation.

Instrumentation
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See also
Concepts in organic chemistry
Laser physics
Laser optics
Laser spectroscopy
Laser ionization
Laser fabrication
Laser medicine
Laser fusion
Civil applications
Military applications
Spectroscopy
Infrared
UV–Vis–NIR
X-ray and
photoelectron
Nucleon
Radiowave
Others
Molecules
Deuterated
molecules
Unconfirmed
Related

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