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Nuclear magnetic resonance (NMR) is a
physical phenomenon A phenomenon ( phenomena), sometimes spelled phaenomenon, is an observable event. The term came into its modern philosophical usage through Immanuel Kant, who contrasted it with the noumenon, which ''cannot'' be directly observed. Kant was he ...
in which nuclei in a strong constant
magnetic field A magnetic field (sometimes called B-field) is a physical field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular ...
are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a frequency characteristic of the magnetic field at the nucleus. This process occurs near
resonance Resonance is a phenomenon that occurs when an object or system is subjected to an external force or vibration whose frequency matches a resonant frequency (or resonance frequency) of the system, defined as a frequency that generates a maximu ...
, 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 Isotopes are distinct nuclear species (or ''nuclides'') of the same chemical element. They have the same atomic number (number of protons in their Atomic nucleus, nuclei) and position in the periodic table (and hence belong to the same chemica ...
involved; in practical applications with static magnetic fields up to ca. 20  tesla, the frequency is similar to VHF and
UHF Ultra high frequency (UHF) is the ITU designation for radio frequencies in the range between 300 megahertz (MHz) and 3 gigahertz (GHz), also known as the decimetre band as the wavelengths range from one meter to one tenth of a meter ...
television broadcasts (60–1000 MHz). NMR results from specific
magnetic Magnetism is the class of physical attributes that occur through a magnetic field, which allows objects to attract or repel each other. Because both electric currents and magnetic moments of elementary particles give rise to a magnetic field, m ...
properties of certain atomic nuclei. High-resolution
nuclear magnetic resonance spectroscopy Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a Spectroscopy, spectroscopic technique based on re-orientation of Atomic nucleus, atomic nuclei with non-zero nuclear sp ...
is widely used to determine the structure of organic molecules in solution and study
molecular physics Molecular physics is the study of the physical properties of molecules and molecular dynamics. The field overlaps significantly with physical chemistry, chemical physics, and quantum chemistry. It is often considered as a sub-field of atomic, mo ...
and
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
s as well as non-crystalline materials. NMR is also routinely used in advanced
medical imaging Medical imaging is the technique and process of imaging the interior of a body for clinical analysis and medical intervention, as well as visual representation of the function of some organs or tissues (physiology). Medical imaging seeks to revea ...
techniques, such as in
magnetic resonance imaging Magnetic resonance imaging (MRI) is a medical imaging technique used in radiology to generate pictures of the anatomy and the physiological processes inside the body. MRI scanners use strong magnetic fields, magnetic field gradients, and ...
(MRI). The original application of NMR to condensed matter physics is nowadays mostly devoted to strongly correlated electron systems. It reveals large many-body couplings by fast broadband detection and should not be confused with solid state NMR, which aims at removing the effect of the same couplings by
Magic Angle Spinning In solid-state NMR spectroscopy, magic-angle spinning (MAS) is a technique routinely used to produce better resolution NMR spectra. MAS NMR consists in spinning the sample (usually at a frequency of 1 to 130  kHz) at the magic angle θm (ca ...
techniques. The most commonly used nuclei are and , although isotopes of many other elements, such as , , and , can be studied by high-field NMR spectroscopy as well. In order to interact with the magnetic field in the spectrometer, the nucleus must have an intrinsic
angular momentum Angular momentum (sometimes called moment of momentum or rotational momentum) is the rotational analog of Momentum, linear momentum. It is an important physical quantity because it is a Conservation law, conserved quantity – the total ang ...
and nuclear magnetic dipole moment. This occurs when an isotope has a nonzero
nuclear spin Nuclear may refer to: Physics Relating to the nucleus of the atom: * Nuclear engineering * Nuclear physics * Nuclear power * Nuclear reactor * Nuclear weapon * Nuclear medicine *Radiation therapy *Nuclear warfare Mathematics * Nuclear space * ...
, meaning an odd number of
protons A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' ( elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an electron (the pro ...
and/or
neutrons The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The neutron was discovered by James Chadwick in 1932, leading to the discovery of nuclear fission in 1938, the f ...
(see
Isotope Isotopes are distinct nuclear species (or ''nuclides'') of the same chemical element. They have the same atomic number (number of protons in their Atomic nucleus, nuclei) and position in the periodic table (and hence belong to the same chemica ...
).
Nuclide Nuclides (or nucleides, from nucleus, also known as nuclear species) are a class of atoms characterized by their number of protons, ''Z'', their number of neutrons, ''N'', and their nuclear energy state. The word ''nuclide'' was coined by the A ...
s with even numbers of both have a total spin of zero and are therefore not NMR-active. In its application to molecules the NMR effect can be observed only in the presence of a static magnetic field. However, in the ordered phases of magnetic materials, very large internal fields are produced at the nuclei of magnetic ions (and of close
ligand In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's el ...
s), which allow NMR to be performed in zero applied field. Additionally, radio-frequency transitions of nuclear spin I > with large enough electric quadrupolar coupling to the
electric field gradient In atomic, molecular, and solid-state physics, the electric field gradient (EFG) measures the rate of change of the electric field at an atomic nucleus generated by the electronic charge distribution and the other nuclei. The EFG couples with the ...
at the nucleus may also be excited in zero applied magnetic field (
nuclear quadrupole resonance Nuclear quadrupole resonance spectroscopy or NQR is a chemical analysis technique related to nuclear magnetic resonance (NMR). Unlike NMR, NQR transitions of nuclei can be detected in the absence of a magnetic field, and for this reason NQR spectro ...
). In the dominant chemistry application, the use of higher fields improves the sensitivity of the method (signal-to-noise ratio scales approximately as the power of with the magnetic field strength) and the spectral resolution. Commercial NMR spectrometers employing
liquid helium Liquid helium is a physical state of helium at very low temperatures at standard atmospheric pressures. Liquid helium may show superfluidity. At standard pressure, the chemical element helium exists in a liquid form only at the extremely low temp ...
cooled
superconducting magnets A superconducting magnet is an electromagnet made from coils of superconducting wire. They must be cooled to cryogenic temperatures during operation. In its superconducting state the wire has no electrical resistance and therefore can conduct much ...
with fields of up to 28 Tesla have been developed and are widely used. It is a key feature of NMR that the resonance frequency of nuclei in a particular sample 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. This effect serves as the basis of
magnetic resonance imaging Magnetic resonance imaging (MRI) is a medical imaging technique used in radiology to generate pictures of the anatomy and the physiological processes inside the body. MRI scanners use strong magnetic fields, magnetic field gradients, and ...
. 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 Radio frequency (RF) is the oscillation rate of an alternating electric current or voltage or of a magnetic, electric or electromagnetic field or mechanical system in the frequency range from around to around . This is roughly between the u ...
(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
Larmor frequency Sir Joseph Larmor (; 11 July 1857 – 19 May 1942) was an Irish mathematician and physicist who made breakthroughs in the understanding of electricity, dynamics, thermodynamics, and the electron theory of matter. His most influential work was ...
and, in itself, does not involve transitions between spin states or energy levels. The two magnetic fields are usually chosen to be
perpendicular In geometry, two geometric objects are perpendicular if they intersect at right angles, i.e. at an angle of 90 degrees or π/2 radians. The condition of perpendicularity may be represented graphically using the '' perpendicular symbol'', � ...
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, usually produced by large currents in
superconducting Superconductivity is a set of physical properties observed in superconductors: materials where electrical resistance vanishes and magnetic fields are expelled from the material. Unlike an ordinary metallic conductor, whose resistance decreases g ...
coils, in order to achieve dispersion of response frequencies and of very high homogeneity and stability in order to deliver
spectral resolution The spectral resolution of a spectrograph, or, more generally, of a frequency spectrum, is a measure of its ability to resolve features in the electromagnetic spectrum. It is usually denoted by \Delta\lambda, and is closely related to the resolvi ...
, the details of which are described by
chemical shift In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of an atomic nucleus relative to a standard in a magnetic field. Often the position and number of chemical shifts are diagnostic of the structure of ...
s, the
Zeeman effect The Zeeman effect () is the splitting of a spectral line into several components in the presence of a static magnetic field. It is caused by the interaction of the magnetic field with the magnetic moment of the atomic electron associated with ...
, 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 Nuclear magnetic resonance (NMR) in the geomagnetic field is conventionally referred to as Earth's field NMR (EFNMR). EFNMR is a special case of low field NMR. When a sample is placed in a constant magnetic field and stimulated (perturbed) by a t ...
), and in several types of
magnetometer A magnetometer is a device that measures magnetic field or magnetic dipole moment. Different types of magnetometers measure the direction, strength, or relative change of a magnetic field at a particular location. A compass is one such device, ...
s.


History

Nuclear magnetic resonance was first described and measured in
molecular beam A molecular beam is produced by allowing a gas at higher pressure to expand through a small orifice into a chamber at lower pressure to form a beam of particles (atoms, free radicals, molecules or ions) moving at approximately equal velocitie ...
s by Isidor Rabi in 1938, by extending the
Stern–Gerlach experiment In quantum physics, the Stern–Gerlach experiment demonstrated that the spatial orientation of angular momentum is quantization (physics), quantized. Thus an Atomic spacing, atomic-scale system was shown to have intrinsically quantum propertie ...
, and in 1944, Rabi was awarded the
Nobel Prize in Physics The Nobel Prize in Physics () is an annual award given by the Royal Swedish Academy of Sciences for those who have made the most outstanding contributions to mankind in the field of physics. It is one of the five Nobel Prizes established by the ...
for this work. In 1946,
Felix Bloch Felix Bloch (; ; 23 October 1905 – 10 September 1983) was a Swiss-American physicist who shared the 1952 Nobel Prize in Physics with Edward Mills Purcell "for their development of new methods for nuclear magnetic precision measurements and di ...
and
Edward Mills Purcell Edward Mills Purcell (August 30, 1912 – March 7, 1997) was an American physicist who shared the 1952 Nobel Prize for Physics for his independent discovery (published 1946) of nuclear magnetic resonance in liquids and in solids. Nuclear magn ...
expanded the technique for use on liquids and solids, for which they shared the Nobel Prize in Physics in 1952. Russell H. Varian filed the "Method and means for correlating nuclear properties of atoms and magnetic fields", on October 21, 1948 and was accepted on July 24, 1951.
Varian Associates Varian Associates was one of the first high-tech companies in Silicon Valley. It was founded in 1948 by Russell H. and Sigurd F. Varian, William Webster Hansen, and Edward Ginzton to sell the klystron, the first vacuum tube which could amp ...
developed the first NMR unit called NMR HR-30 in 1952. Purcell had worked on the development of
radar Radar is a system that uses radio waves to determine the distance ('' ranging''), direction ( azimuth and elevation angles), and radial velocity of objects relative to the site. It is a radiodetermination method used to detect and track ...
during
World War II World War II or the Second World War (1 September 1939 – 2 September 1945) was a World war, global conflict between two coalitions: the Allies of World War II, Allies and the Axis powers. World War II by country, Nearly all of the wo ...
at the
Massachusetts Institute of Technology The Massachusetts Institute of Technology (MIT) is a Private university, private research university in Cambridge, Massachusetts, United States. Established in 1861, MIT has played a significant role in the development of many areas of moder ...
's
Radiation Laboratory The Radiation Laboratory, commonly called the Rad Lab, was a microwave and radar research laboratory located at the Massachusetts Institute of Technology (MIT) in Cambridge, Massachusetts. It was first created in October 1940 and operated until 3 ...
. His work during that project on the production and detection of radio frequency power and on the absorption of such RF power by matter laid the foundation for his discovery of NMR in bulk matter. Rabi, Bloch, and Purcell observed that magnetic nuclei, like and , could absorb RF energy when placed in a magnetic field and when the RF was of a frequency specific to the identity of the nuclei. When this absorption occurs, the nucleus is described as being ''in resonance''. Different atomic nuclei within a molecule resonate at different (radio) frequencies in the same applied static magnetic field, due to various local magnetic fields. The observation of such magnetic resonance frequencies of the nuclei present in a molecule makes it possible to determine essential chemical and structural information about the molecule. The improvements of the NMR method benefited from the development of electromagnetic technology and advanced
electronics Electronics is a scientific and engineering discipline that studies and applies the principles of physics to design, create, and operate devices that manipulate electrons and other Electric charge, electrically charged particles. It is a subfield ...
and their introduction into civilian use. Originally as a research tool it was limited primarily to dynamic nuclear polarization, by the work of Anatole Abragam and Albert Overhauser, and to
condensed matter physics Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid State of matter, phases, that arise from electromagnetic forces between atoms and elec ...
, where it produced one of the first demonstrations of the validity of the
BCS theory In physics, the Bardeen–Cooper–Schrieffer (BCS) theory (named after John Bardeen, Leon Cooper, and John Robert Schrieffer) is the first microscopic theory of superconductivity since Heike Kamerlingh Onnes's 1911 discovery. The theory descr ...
of
superconductivity Superconductivity is a set of physical properties observed in superconductors: materials where Electrical resistance and conductance, electrical resistance vanishes and Magnetic field, magnetic fields are expelled from the material. Unlike an ord ...
by the observation by Charles Slichter of the Hebel-Slichter effect. It soon showed its potential in
organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...
, where NMR has become indispensable, and by the 1990s improvement in the sensitivity and resolution of NMR spectroscopy resulted in its broad use in
analytical chemistry Analytical skill, Analytical chemistry studies and uses instruments and methods to Separation process, separate, identify, and Quantification (science), quantify matter. In practice, separation, identification or quantification may constitute t ...
,
biochemistry Biochemistry, or biological chemistry, is the study of chemical processes within and relating to living organisms. A sub-discipline of both chemistry and biology, biochemistry may be divided into three fields: structural biology, enzymology, a ...
and
materials science Materials science is an interdisciplinary field of researching and discovering materials. Materials engineering is an engineering field of finding uses for materials in other fields and industries. The intellectual origins of materials sci ...
. In the 2020s zero- to ultralow-field nuclear magnetic resonance ( ZULF NMR), a form of
spectroscopy Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum. Spectro ...
that provides abundant analytical results without the need for large
magnetic field A magnetic field (sometimes called B-field) is a physical field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular ...
s, was developed. It is combined with a special technique that makes it possible to hyperpolarize
atomic nuclei The atomic nucleus is the small, dense region consisting of protons and neutrons at the center of an atom, discovered in 1911 by Ernest Rutherford at the University of Manchester based on the 1909 Geiger–Marsden gold foil experiment. Aft ...
.


Theory of nuclear magnetic resonance


Nuclear spins and magnets

All nucleons, that is
neutrons The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The neutron was discovered by James Chadwick in 1932, leading to the discovery of nuclear fission in 1938, the f ...
and
protons A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' ( elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an electron (the pro ...
, composing any atomic
nucleus Nucleus (: nuclei) is a Latin word for the seed inside a fruit. It most often refers to: *Atomic nucleus, the very dense central region of an atom *Cell nucleus, a central organelle of a eukaryotic cell, containing most of the cell's DNA Nucleu ...
, have the intrinsic quantum property of
spin Spin or spinning most often refers to: * Spin (physics) or particle spin, a fundamental property of elementary particles * Spin quantum number, a number which defines the value of a particle's spin * Spinning (textiles), the creation of yarn or thr ...
, an intrinsic
angular momentum Angular momentum (sometimes called moment of momentum or rotational momentum) is the rotational analog of Momentum, linear momentum. It is an important physical quantity because it is a Conservation law, conserved quantity – the total ang ...
analogous to the classical angular momentum of a spinning sphere. The overall spin of the nucleus is determined by the
spin quantum number In physics and chemistry, the spin quantum number is a quantum number (designated ) that describes the intrinsic angular momentum (or spin angular momentum, or simply ''spin'') of an electron or other particle. It has the same value for all ...
''S''. If the numbers of both the protons and neutrons in a given
nuclide Nuclides (or nucleides, from nucleus, also known as nuclear species) are a class of atoms characterized by their number of protons, ''Z'', their number of neutrons, ''N'', and their nuclear energy state. The word ''nuclide'' was coined by the A ...
are even then , i.e. there is no overall spin. Then, just as electrons pair up in nondegenerate
atomic orbital In quantum mechanics, an atomic orbital () is a Function (mathematics), function describing the location and Matter wave, wave-like behavior of an electron in an atom. This function describes an electron's Charge density, charge distribution a ...
s, so do even numbers of protons or even numbers of neutrons (both of which are also spin- particles and hence
fermion In particle physics, a fermion is a subatomic particle that follows Fermi–Dirac statistics. Fermions have a half-integer spin (spin 1/2, spin , Spin (physics)#Higher spins, spin , etc.) and obey the Pauli exclusion principle. These particles i ...
s), giving zero overall spin. However, an unpaired proton and unpaired neutron will have a lower energy when their spins are parallel, not anti-parallel. This parallel spin alignment of distinguishable particles does not violate the
Pauli exclusion principle In quantum mechanics, the Pauli exclusion principle (German: Pauli-Ausschlussprinzip) states that two or more identical particles with half-integer spins (i.e. fermions) cannot simultaneously occupy the same quantum state within a system that o ...
. The lowering of energy for parallel spins has to do with the
quark A quark () is a type of elementary particle and a fundamental constituent of matter. Quarks combine to form composite particles called hadrons, the most stable of which are protons and neutrons, the components of atomic nucleus, atomic nuclei ...
structure of these two nucleons. As a result, the spin
ground state The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state ...
for the deuteron (the nucleus of
deuterium Deuterium (hydrogen-2, symbol H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, H. The deuterium nucleus (deuteron) contains one proton and one neutron, whereas the far more c ...
, the 2H isotope of hydrogen), which has only a proton and a neutron, corresponds to a spin value of 1, ''not of zero''. On the other hand, because of the Pauli exclusion principle, the
tritium Tritium () or hydrogen-3 (symbol T or H) is a rare and radioactive isotope of hydrogen with a half-life of ~12.33 years. The tritium nucleus (t, sometimes called a ''triton'') contains one proton and two neutrons, whereas the nucleus of the ...
isotope of hydrogen must have a pair of anti-parallel spin neutrons (of total spin zero for the neutron spin-pair), plus a proton of spin . Therefore, the tritium total nuclear spin value is again , just like the simpler, abundant hydrogen isotope, 1H nucleus (the ''
proton A proton is a stable subatomic particle, symbol , Hydron (chemistry), H+, or 1H+ with a positive electric charge of +1 ''e'' (elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an e ...
''). The NMR absorption frequency for tritium is also similar to that of 1H. In many other cases of ''non-radioactive'' nuclei, the overall spin is also non-zero and may have a contribution from the orbital angular momentum of the unpaired nucleon. For example, the nucleus has an overall spin value . A non-zero spin \vec is associated with a non-zero
magnetic dipole moment In electromagnetism, the magnetic moment or magnetic dipole moment is the combination of strength and orientation of a magnet or other object or system that exerts a magnetic field. The magnetic dipole moment of an object determines the magnitude ...
, \vec , via the relation \vec = \gamma \vec where ''γ'' is the
gyromagnetic ratio In physics, the gyromagnetic ratio (also sometimes known as the magnetogyric ratio in other disciplines) of a particle or system is the ratio of its magnetic moment to its angular momentum, and it is often denoted by the symbol , gamma. Its SI u ...
. Classically, this corresponds to the proportionality between the angular momentum and the magnetic dipole moment of a spinning charged sphere, both of which are vectors parallel to the rotation axis whose length increases proportional to the spinning frequency. It is the magnetic moment and its interaction with magnetic fields that allows the observation of NMR signal associated with transitions between nuclear spin levels during resonant RF irradiation or caused by Larmor precession of the average magnetic moment after resonant irradiation. Nuclides with even numbers of both protons and neutrons have zero nuclear magnetic dipole moment and hence do not exhibit NMR signal. For instance, is an example of a nuclide that produces no NMR signal, whereas , , and are nuclides that do exhibit NMR spectra. The last two nuclei have spin ''S'' > and are therefore quadrupolar nuclei.
Electron spin resonance Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spin ...
(ESR) is a related technique in which transitions between
electron The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
ic rather than nuclear spin levels are detected. The basic principles are similar but the instrumentation, data analysis, and detailed theory are significantly different. Moreover, there is a much smaller number of molecules and materials with unpaired electron spins that exhibit ESR (or
electron paramagnetic resonance Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spin ...
(EPR)) absorption than those that have NMR absorption spectra. On the other hand, ESR has much higher signal per spin than NMR does.


Values of spin angular momentum

Nuclear
spin Spin or spinning most often refers to: * Spin (physics) or particle spin, a fundamental property of elementary particles * Spin quantum number, a number which defines the value of a particle's spin * Spinning (textiles), the creation of yarn or thr ...
is an intrinsic
angular momentum Angular momentum (sometimes called moment of momentum or rotational momentum) is the rotational analog of Momentum, linear momentum. It is an important physical quantity because it is a Conservation law, conserved quantity – the total ang ...
that is quantized. This means that the magnitude of this angular momentum is quantized (i.e. ''S'' can only take on a restricted range of values), and also that the x, y, and z-components of the angular momentum are quantized, being restricted to integer or half-integer multiples of ''ħ'', the reduced
Planck constant The Planck constant, or Planck's constant, denoted by h, is a fundamental physical constant of foundational importance in quantum mechanics: a photon's energy is equal to its frequency multiplied by the Planck constant, and the wavelength of a ...
. The integer or half-integer quantum number associated with the spin component along the z-axis or the applied magnetic field is known as the
magnetic quantum number In atomic physics, a magnetic quantum number is a quantum number used to distinguish quantum states of an electron or other particle according to its angular momentum along a given axis in space. The orbital magnetic quantum number ( or ) disting ...
, ''m'', and can take values from +''S'' to −''S'', in integer steps. Hence for any given nucleus, there are a total of angular momentum states. The ''z''-component of the angular momentum vector ( \vec ) is therefore . The ''z''-component of the magnetic moment is simply: \mu_z = \gamma S_z = \gamma m\hbar.


Spin energy in a magnetic field

Consider nuclei with a spin of one-half, like , or . Each nucleus has two linearly independent spin states, with ''m'' = or ''m'' = − (also referred to as spin-up and spin-down, or sometimes α and β spin states, respectively) for the z-component of spin. In the absence of a magnetic field, these states are degenerate; that is, they have the same energy. Hence the number of nuclei in these two states will be essentially equal at
thermal equilibrium Two physical systems are in thermal equilibrium if there is no net flow of thermal energy between them when they are connected by a path permeable to heat. Thermal equilibrium obeys the zeroth law of thermodynamics. A system is said to be in t ...
. If a nucleus with spin is placed in a magnetic field, however, the two states no longer have the same energy as a result of the interaction between the nuclear magnetic dipole moment and the external magnetic field. The
energy Energy () is the physical quantity, quantitative physical property, property that is transferred to a physical body, body or to a physical system, recognizable in the performance of Work (thermodynamics), work and in the form of heat and l ...
of a magnetic dipole moment \vec in a magnetic field B0 is given by: E = -\vec \cdot \mathbf_0 = -\mu_x B_-\mu_y B_ - \mu_z B_ . Usually the ''z''-axis is chosen to be along B0, and the above expression reduces to: E = -\mu_\mathrm B_0 \, , or alternatively: E = -\gamma m\hbar B_0 \, . As a result, the different nuclear spin states have different energies in a non-zero magnetic field. In less formal language, we can talk about the two spin states of a spin as being ''aligned'' either with or against the magnetic field. If ''γ'' is positive (true for most isotopes used in NMR) then ("spin up") is the lower energy state. The energy difference between the two states is: \Delta = \gamma \hbar B_0 \, , and this results in a small population bias favoring the lower energy state in thermal equilibrium. With more spins pointing up than down, a net spin magnetization along the magnetic field B0 results.


Precession of the spin magnetization

A central concept in NMR is the precession of the spin magnetization around the magnetic field at the nucleus, with the angular frequency \omega = -\gamma B where \omega = 2 \pi \nu relates to the oscillation frequency \nu and ''B'' is the magnitude of the field.C. Cohen-Tannoudji, B. Diu, F. Laloe, ''Quantum Mechanics'', Vol. 1, Wiley VCH, 1977. This means that the spin magnetization, which is proportional to the sum of the spin vectors of nuclei in magnetically equivalent sites (the
expectation value In probability theory, the expected value (also called expectation, expectancy, expectation operator, mathematical expectation, mean, expectation value, or first moment) is a generalization of the weighted average. Informally, the expected va ...
of the spin vector in quantum mechanics), moves on a cone around the B field. This is analogous to the precessional motion of the axis of a tilted spinning top around the gravitational field. In quantum mechanics, \omega is the ''Bohr frequency'' \Delta/\hbar of the S_x and S_y expectation values. Precession of non-equilibrium magnetization in the applied magnetic field B0 occurs with the Larmor frequency \omega_L = 2 \pi \nu_L = -\gamma B_0, without change in the populations of the energy levels because energy is constant (time-independent Hamiltonian).


Magnetic resonance and radio-frequency pulses

A perturbation of nuclear spin orientations from equilibrium will occur only when an oscillating magnetic field is applied whose frequency ''ν''rf sufficiently closely matches the
Larmor precession Sir Joseph Larmor (; 11 July 1857 – 19 May 1942) was an Irish mathematician and physicist who made breakthroughs in the understanding of electricity, dynamics, thermodynamics, and the electron theory of matter. His most influential work was ...
frequency ''ν''L of the nuclear magnetization. The populations of the spin-up and -down energy levels then undergo Rabi oscillations, which are analyzed most easily in terms of precession of the spin magnetization around the effective magnetic field in a reference frame rotating with the frequency ''ν''rf.A. Abragam, ''The Principles of Nuclear Magnetism'', Ch. 2, Oxford Clarendon Press, 1961. The stronger the oscillating field, the faster the Rabi oscillations or the precession around the effective field in the rotating frame. After a certain time on the order of 2–1000 microseconds, a resonant RF pulse flips the spin magnetization to the transverse plane, i.e. it makes an angle of 90° with the constant magnetic field B0 ("90° pulse"), while after a twice longer time, the initial magnetization has been inverted ("180° pulse"). It is the transverse magnetization generated by a resonant oscillating field which is usually detected in NMR, during application of the relatively weak RF field in old-fashioned continuous-wave NMR, or after the relatively strong RF pulse in modern pulsed NMR.


Chemical shielding

It might appear from the above that all nuclei of the same nuclide (and hence the same ''γ'') would resonate at exactly the same frequency but this is not the case. The most important perturbation of the NMR frequency for applications of NMR is the "shielding" effect of the shells of electrons surrounding the nucleus. Electrons, similar to the nucleus, are also charged and rotate with a spin to produce a magnetic field opposite to the applied magnetic field. In general, this electronic shielding reduces the magnetic field ''at the nucleus'' (which is what determines the NMR frequency). As a result, the frequency required to achieve resonance is also reduced. This shift in the NMR frequency due to the electronic molecular orbital coupling to the external magnetic field is called
chemical shift In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of an atomic nucleus relative to a standard in a magnetic field. Often the position and number of chemical shifts are diagnostic of the structure of ...
, and it explains why NMR is able to probe the chemical structure of molecules, which depends on the electron density distribution in the corresponding molecular orbitals. If a nucleus in a specific chemical group is shielded to a higher degree by a higher electron density of its surrounding molecular orbitals, then its NMR frequency will be shifted "upfield" (that is, a lower chemical shift), whereas if it is less shielded by such surrounding electron density, then its NMR frequency will be shifted "downfield" (that is, a higher chemical shift). Unless the local
symmetry Symmetry () in everyday life refers to a sense of harmonious and beautiful proportion and balance. In mathematics, the term has a more precise definition and is usually used to refer to an object that is Invariant (mathematics), invariant und ...
of such molecular orbitals is very high (leading to "isotropic" shift), the
shielding effect In chemistry, the shielding effect sometimes referred to as atomic shielding or electron shielding describes the attraction between an electron and the nucleus in any atom with more than one electron. The shielding effect can be defined as a r ...
will depend on the orientation of the molecule with respect to the external field (B0). In
solid-state NMR Solid-state nuclear magnetic resonance (ssNMR) is a spectroscopy technique used to characterize atomic-level structure and dynamics in solid materials. ssNMR spectra are broader due to nuclear spin interactions which can be categorized as dipolar ...
spectroscopy,
magic angle spinning In solid-state NMR spectroscopy, magic-angle spinning (MAS) is a technique routinely used to produce better resolution NMR spectra. MAS NMR consists in spinning the sample (usually at a frequency of 1 to 130  kHz) at the magic angle θm (ca ...
is required to average out this orientation dependence in order to obtain frequency values at the average or isotropic chemical shifts. This is unnecessary in conventional NMR investigations of molecules in solution, since rapid "molecular tumbling" averages out the chemical shift anisotropy (CSA). In this case, the "average" chemical shift (ACS) or isotropic chemical shift is often simply referred to as the chemical shift.


Radiation Damping

In 1949, Suryan first suggested that the interaction between a radiofrequency coil and a sample's bulk magnetization could explain why experimental observations of relaxation times differed from theoretical predictions. Building on this idea, Bloembergen and Pound further developed Suryan's hypothesis by mathematically integrating the Maxwell–Bloch equations, a process through which they introduced the concept of "radiation damping." Radiation damping (RD) in
Nuclear Magnetic Resonance Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
(NMR) is an intrinsic phenomenon observed in many high-field NMR experiments, especially relevant in systems with high concentrations of nuclei like protons or fluorine. RD occurs when transverse bulk magnetization from the sample, following a radio frequency pulse, induces an
electromagnetic field An electromagnetic field (also EM field) is a physical field, varying in space and time, that represents the electric and magnetic influences generated by and acting upon electric charges. The field at any point in space and time can be regarde ...
(emf) in the receiver coil of the NMR spectrometer. This generates an oscillating current and a non-linear induced transverse magnetic field which returns the spin system to equilibrium faster than other mechanisms of relaxation. RD can result in line broadening and measurement of a shorter spin-lattice relaxation time (T_). For instance, a sample of water in a 400 MHz NMR spectrometer will have T_ around 20 ms, whereas its T_ is hundreds of milliseconds. This effect is often described using modified Bloch equations that include terms for radiation damping alongside the conventional relaxation terms. The longitudinal relaxation time of radiation damping (T_) is given by the equation T_=\frac where \gamma is the
gyromagnetic ratio In physics, the gyromagnetic ratio (also sometimes known as the magnetogyric ratio in other disciplines) of a particle or system is the ratio of its magnetic moment to its angular momentum, and it is often denoted by the symbol , gamma. Its SI u ...
, \mu_0 is the
magnetic permeability In electromagnetism, permeability is the measure of magnetization produced in a material in response to an applied magnetic field. Permeability is typically represented by the (italicized) Greek letter ''μ''. It is the ratio of the magnetic ...
, M_0 is the equilibrium magnetization per unit volume, Q is the filling factor of the probe which is the ratio of the probe coil volume to the sample volume enclosed, Q=\frac is the quality factor of the probe, and , L, and R are the resonance frequency, inductance, and resistance of the coil, respectively. The quantification of line broadening due to radiation damping can be determined by measuring the \Delta v_ and use equation T_^=\frac \Delta v_ Radiation damping in NMR is influenced significantly by system parameters. It is notably more prominent in systems where the NMR probe possesses a high quality factor (Q) and a high filling factor , resulting in a strong coupling between the probe coil and the sample. The phenomenon is also impacted by the concentration of the nuclei within the sample and their magnetic moments, which can intensify the effects of radiation damping. The strength of the magnetic field is inversely proportional to the lifetime of RD. The impact of radiation damping on NMR signals is multifaceted. It can accelerate the decay of the NMR signal faster than intrinsic relaxation processes would suggest. This acceleration can complicate the interpretation of NMR spectra by causing broadening of spectral lines, distorting multiplet structures, and introducing artifacts, especially in high-resolution NMR scenarios. Such effects make it challenging to obtain clear and accurate data without considering the influence of radiation damping. To mitigate these effects, various strategies are employed in NMR spectroscopy. These methods majorly stem from hardware or software. Hardware modifications including RF feed-circuit and Q-factor switches reduce the feedback loop between the sample magnetization and the electromagnetic field induced by the coil and function successfully. Other approaches such as designing selective pulse sequences also effectively manage the fields induced by radiation damping. These approaches aim to control and limit the disruptive effects of radiation damping during NMR experiments and all approaches are successful in eliminating RD to a fairly large extent. Overall, understanding and managing radiation damping is crucial for obtaining high-quality NMR data, especially in modern high-field spectrometers where the effects can be significant due to the increased sensitivity and resolution.


Relaxation

The process of population relaxation refers to nuclear spins that return to thermodynamic equilibrium in the magnet. This process is also called ''T''1, " spin-lattice" or "longitudinal magnetic" relaxation, where ''T''1 refers to the mean time for an individual nucleus to return to its thermal equilibrium state of the spins. After the nuclear spin population has relaxed, it can be probed again, since it is in the initial, equilibrium (mixed) state. The precessing nuclei can also fall out of alignment with each other and gradually stop producing a signal. This is called ''T''2, " spin-spin" or ''transverse relaxation''. Because of the difference in the actual relaxation mechanisms involved (for example, intermolecular versus intramolecular magnetic dipole-dipole interactions), ''T''1 is usually (except in rare cases) longer than ''T''2 (that is, slower spin-lattice relaxation, for example because of smaller dipole-dipole interaction effects). In practice, the value of ''T''2*, which is the actually observed decay time of the observed NMR signal, or free induction decay (to of the initial amplitude immediately after the resonant RF pulse), also depends on the static magnetic field inhomogeneity, which may be quite significant. (There is also a smaller but significant contribution to the observed FID shortening from the RF inhomogeneity of the resonant pulse). In the corresponding FT-NMR spectrum—meaning the
Fourier transform In mathematics, the Fourier transform (FT) is an integral transform that takes a function as input then outputs another function that describes the extent to which various frequencies are present in the original function. The output of the tr ...
of the free induction decay— the width of the NMR signal in frequency units is inversely related to the ''T''2* time. Thus, a nucleus with a long ''T''2* relaxation time gives rise to a very sharp NMR peak in the FT-NMR spectrum for a very homogeneous ( "well-shimmed") static magnetic field, whereas nuclei with shorter ''T''2* values give rise to broad FT-NMR peaks even when the magnet is shimmed well. Both ''T''1 and ''T''2 depend on the rate of molecular motions as well as the gyromagnetic ratios of both the resonating and their strongly interacting, next-neighbor nuclei that are not at resonance. A Hahn echo decay experiment can be used to measure the dephasing time, as shown in the animation. The size of the echo is recorded for different spacings of the two pulses. This reveals the decoherence that is not refocused by the 180° pulse. In simple cases, an
exponential decay A quantity is subject to exponential decay if it decreases at a rate proportional to its current value. Symbolically, this process can be expressed by the following differential equation, where is the quantity and (lambda Lambda (; uppe ...
is measured which is described by the ''T''2 time.


NMR spectroscopy

NMR spectroscopy is one of the principal techniques used to obtain physical, chemical, electronic and structural information about
molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
s due to the chemical shift of the resonance frequencies of the nuclear spins in the sample. Peak splittings due to J- or dipolar couplings between nuclei are also useful. NMR spectroscopy can provide detailed and quantitative information on the functional groups, topology, dynamics and three-dimensional structure of molecules in solution and the solid state. Since the area under an NMR peak is usually proportional to the number of spins involved, peak integrals can be used to determine composition quantitatively. Structure and molecular dynamics can be studied (with or without "magic angle" spinning (MAS)) by NMR of quadrupolar nuclei (that is, with spin ) even in the presence of magnetic "
dipole In physics, a dipole () is an electromagnetic phenomenon which occurs in two ways: * An electric dipole moment, electric dipole deals with the separation of the positive and negative electric charges found in any electromagnetic system. A simple ...
-dipole" interaction broadening (or simply, dipolar broadening), which is always much smaller than the quadrupolar interaction strength because it is a magnetic vs. an electric interaction effect. Additional structural and chemical information may be obtained by performing double-quantum NMR experiments for pairs of spins or quadrupolar nuclei such as . Furthermore, nuclear magnetic resonance is one of the techniques that has been used to design quantum automata, and also build elementary
quantum computer A quantum computer is a computer that exploits quantum mechanical phenomena. On small scales, physical matter exhibits properties of both particles and waves, and quantum computing takes advantage of this behavior using specialized hardware. ...
s.


Continuous-wave (CW) spectroscopy

In the first few decades of nuclear magnetic resonance, spectrometers used a technique known as
continuous-wave A continuous wave or continuous waveform (CW) is an electromagnetic wave of constant amplitude and frequency, typically a sine wave, that for mathematical analysis is considered to be of infinite duration. It may refer to e.g. a laser or particle ...
(CW) spectroscopy, where the transverse spin magnetization generated by a weak oscillating magnetic field is recorded as a function of the oscillation frequency or static field strength ''B''0. When the oscillation frequency matches the nuclear resonance frequency, the transverse magnetization is maximized and a peak is observed in the spectrum. Although NMR spectra could be, and have been, obtained using a fixed constant magnetic field and sweeping the frequency of the oscillating magnetic field, it was more convenient to use a fixed frequency source and vary the current (and hence magnetic field) in an
electromagnet An electromagnet is a type of magnet in which the magnetic field is produced by an electric current. Electromagnets usually consist of wire (likely copper) wound into a electromagnetic coil, coil. A current through the wire creates a magnetic ...
to observe the resonant absorption signals. This is the origin of the counterintuitive, but still common, "high field" and "low field" terminology for low frequency and high frequency regions, respectively, of the NMR spectrum. As of 1996, CW instruments were still used for routine work because the older instruments were cheaper to maintain and operate, often operating at 60 MHz with correspondingly weaker (non-superconducting) electromagnets cooled with water rather than liquid helium. One radio coil operated continuously, sweeping through a range of frequencies, while another
orthogonal In mathematics, orthogonality (mathematics), orthogonality is the generalization of the geometric notion of ''perpendicularity''. Although many authors use the two terms ''perpendicular'' and ''orthogonal'' interchangeably, the term ''perpendic ...
coil, designed not to receive radiation from the transmitter, received signals from nuclei that reoriented in solution. As of 2014, low-end refurbished 60 MHz and 90 MHz systems were sold as FT-NMR instruments, and in 2010 the "average workhorse" NMR instrument was configured for 300 MHz. CW spectroscopy is inefficient in comparison with
Fourier analysis In mathematics, Fourier analysis () is the study of the way general functions may be represented or approximated by sums of simpler trigonometric functions. Fourier analysis grew from the study of Fourier series, and is named after Joseph Fo ...
techniques (see below) since it probes the NMR response at individual frequencies or field strengths in succession. Since the NMR signal is intrinsically weak, the observed spectrum suffers from a poor
signal-to-noise ratio Signal-to-noise ratio (SNR or S/N) is a measure used in science and engineering that compares the level of a desired signal to the level of background noise. SNR is defined as the ratio of signal power to noise power, often expressed in deci ...
. This can be mitigated by signal averaging, i.e. adding the spectra from repeated measurements. While the NMR signal is the same in each scan and so adds linearly, the
random noise In electronics, noise is an unwanted disturbance in an electrical signal. Noise generated by electronic devices varies greatly as it is produced by several different effects. In particular, noise is inherent in physics and central to thermod ...
adds more slowly – proportional to the
square root In mathematics, a square root of a number is a number such that y^2 = x; in other words, a number whose ''square'' (the result of multiplying the number by itself, or y \cdot y) is . For example, 4 and −4 are square roots of 16 because 4 ...
of the number of spectra added (see
random walk In mathematics, a random walk, sometimes known as a drunkard's walk, is a stochastic process that describes a path that consists of a succession of random steps on some Space (mathematics), mathematical space. An elementary example of a rand ...
). Hence the overall signal-to-noise ratio increases as the square-root of the number of spectra measured. However, monitoring an NMR signal at a single frequency as a function of time may be better suited for kinetic studies than pulsed Fourier-transform NMR spectrosocopy.


Fourier-transform spectroscopy

Most applications of NMR involve full NMR spectra, that is, the intensity of the NMR signal as a function of frequency. Early attempts to acquire the NMR spectrum more efficiently than simple CW methods involved illuminating the target simultaneously with more than one frequency. A revolution in NMR occurred when short radio-frequency pulses began to be used, with a frequency centered at the middle of the NMR spectrum. In simple terms, a short pulse of a given "carrier" frequency "contains" a range of frequencies centered about the
carrier frequency In telecommunications, a carrier wave, carrier signal, or just carrier, is a periodic waveform (usually sinusoidal) that conveys information through a process called ''modulation''. One or more of the wave's properties, such as amplitude or fre ...
, with the range of excitation (
bandwidth Bandwidth commonly refers to: * Bandwidth (signal processing) or ''analog bandwidth'', ''frequency bandwidth'', or ''radio bandwidth'', a measure of the width of a frequency range * Bandwidth (computing), the rate of data transfer, bit rate or thr ...
) being inversely proportional to the pulse duration, i.e. the
Fourier transform In mathematics, the Fourier transform (FT) is an integral transform that takes a function as input then outputs another function that describes the extent to which various frequencies are present in the original function. The output of the tr ...
of a short pulse contains contributions from all the frequencies in the neighborhood of the principal frequency. The restricted range of the NMR frequencies for most light spin- nuclei made it relatively easy to use short (1 - 100 microsecond) radio frequency pulses to excite the entire NMR spectrum. Applying such a pulse to a set of nuclear spins simultaneously excites all the single-quantum NMR transitions. In terms of the net magnetization vector, this corresponds to tilting the magnetization vector away from its equilibrium position (aligned along the external magnetic field). The out-of-equilibrium magnetization vector then precesses about the external magnetic field vector at the NMR frequency of the spins. This oscillating magnetization vector induces a voltage in a nearby pickup coil, creating an electrical signal oscillating at the NMR frequency. This signal is known as the free induction decay (FID), and it contains the sum of the NMR responses from all the excited spins. In order to obtain the frequency-domain NMR
spectrum A spectrum (: spectra or spectrums) is a set of related ideas, objects, or properties whose features overlap such that they blend to form a continuum. The word ''spectrum'' was first used scientifically in optics to describe the rainbow of co ...
(NMR absorption intensity vs. NMR frequency) this time-domain signal (intensity vs. time) must be Fourier transformed. Fortunately, the development of Fourier transform (FT) NMR coincided with the development of
digital computer A computer is a machine that can be programmed to automatically carry out sequences of arithmetic or logical operations (''computation''). Modern digital electronic computers can perform generic sets of operations known as ''programs'', wh ...
s and the digital
fast Fourier transform A fast Fourier transform (FFT) is an algorithm that computes the discrete Fourier transform (DFT) of a sequence, or its inverse (IDFT). A Fourier transform converts a signal from its original domain (often time or space) to a representation in ...
(FFT). Fourier methods can be applied to many types of spectroscopy. Richard R. Ernst was one of the pioneers of pulsed NMR and won a
Nobel Prize in chemistry The Nobel Prize in Chemistry () is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outst ...
in 1991 for his work on Fourier Transform NMR and his development of multi-dimensional NMR spectroscopy.


Multi-dimensional NMR spectroscopy

The use of pulses of different durations, frequencies, or shapes in specifically designed patterns or ''pulse sequences'' allows production of a spectrum that contains many different types of information about the molecules in the sample. In multi-dimensional nuclear magnetic resonance spectroscopy, there are at least two pulses: one leads to the directly detected signal and the others affect the starting magnetization and spin state prior to it. The full analysis involves repeating the sequence with the pulse timings systematically varied in order to probe the oscillations of the spin system are point by point in the time domain. Multidimensional Fourier transformation of the multidimensional time signal yields the multidimensional spectrum. In two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), there will be one systematically varied time period in the sequence of pulses, which will modulate the intensity or phase of the detected signals. In 3D-NMR, two time periods will be varied independently, and in 4D-NMR, three will be varied. There are many such experiments. In some, fixed time intervals allow (among other things) magnetization transfer between nuclei and, therefore, the detection of the kinds of nuclear–nuclear interactions that allowed for the magnetization transfer. Interactions that can be detected are usually classified into two kinds. There are ''through-bond'' and ''through-space'' interactions. Through-bond interactions relate to structural connectivity of the atoms and provide information about which ones are directly connected to each other, connected by way of a single other intermediate atom, etc. Through-space interactions relate to actual geometric distances and angles, including effects of dipolar coupling and the
nuclear Overhauser effect The nuclear Overhauser effect (NOE) is the transfer of spin polarization, nuclear spin polarization from one population of Spin (physics), spin-active nuclei (e.g. 1H, 13C, 15N etc.) to another via Relaxation (NMR), cross-relaxation. A phenomenolog ...
. Although the fundamental concept of 2D-FT NMR was proposed by Jean Jeener from the Free University of Brussels at an international conference, this idea was largely developed by Richard Ernst, who won the 1991
Nobel prize in Chemistry The Nobel Prize in Chemistry () is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outst ...
for his work in FT NMR, including multi-dimensional FT NMR, and especially 2D-FT NMR of small molecules. Multi-dimensional FT NMR experiments were then further developed into powerful methodologies for studying molecules in solution, in particular for the determination of the structure of
biopolymer Biopolymers are natural polymers produced by the cells of living organisms. Like other polymers, biopolymers consist of monomeric units that are covalently bonded in chains to form larger molecules. There are three main classes of biopolymers, ...
s such as
protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residue (biochemistry), residues. Proteins perform a vast array of functions within organisms, including Enzyme catalysis, catalysing metab ...
s or even small
nucleic acid Nucleic acids are large biomolecules that are crucial in all cells and viruses. They are composed of nucleotides, which are the monomer components: a pentose, 5-carbon sugar, a phosphate group and a nitrogenous base. The two main classes of nuclei ...
s. In 2002 Kurt Wüthrich shared the
Nobel Prize in Chemistry The Nobel Prize in Chemistry () is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outst ...
(with John Bennett Fenn and
Koichi Tanaka is a Japanese electrical engineer who shared the Nobel Prize in Chemistry in 2002 for developing a novel method for mass spectrometric analyses of biological macromolecules with John Bennett Fenn and Kurt Wüthrich (the latter for work in N ...
) for his work with protein FT NMR in solution.


Solid-state NMR spectroscopy

This technique complements
X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...
in that it is frequently applicable to molecules in an amorphous or liquid-crystalline state, whereas crystallography, as the name implies, is performed on molecules in a crystalline phase. In electronically conductive materials, the Knight shift of the resonance frequency can provide information on the mobile charge carriers. Though nuclear magnetic resonance is used to study the structure of solids, extensive atomic-level structural detail is more challenging to obtain in the solid state. Due to broadening by chemical shift anisotropy (CSA) and dipolar couplings to other nuclear spins, without special techniques such as MAS or dipolar decoupling by RF pulses, the observed spectrum is often only a broad Gaussian band for non-quadrupolar spins in a solid. Professor Raymond Andrew at the
University of Nottingham The University of Nottingham is a public research university in Nottingham, England. It was founded as University College Nottingham in 1881, and was granted a royal charter in 1948. Nottingham's main campus (University Park Campus, Nottingh ...
in the UK pioneered the development of high-resolution
solid-state nuclear magnetic resonance Solid-state nuclear magnetic resonance (ssNMR) is a spectroscopy technique used to characterize atomic-level structure and dynamics in solid materials. ssNMR spectra are broader due to nuclear spin interactions which can be categorized as dipolar ...
. He was the first to report the introduction of the MAS (magic angle sample spinning; MASS) technique that allowed him to achieve spectral resolution in solids sufficient to distinguish between chemical groups with either different chemical shifts or distinct Knight shifts. In MASS, the sample is spun at several kilohertz around an axis that makes the so-called
magic angle The magic angle is a precisely defined angle, the value of which is approximately 54.7356°. The magic angle is a root of a second-order Legendre polynomial, , and so any interaction which depends on this second-order Legendre polynomial vanishes ...
''θ''m (which is ~54.74°, where 3cos2''θ''m-1 = 0) with respect to the direction of the static magnetic field B0; as a result of such magic angle sample spinning, the broad chemical shift anisotropy bands are averaged to their corresponding average (isotropic) chemical shift values. Correct alignment of the sample rotation axis as close as possible to ''θ''m is essential for cancelling out the chemical-shift anisotropy broadening. There are different angles for the sample spinning relative to the applied field for the averaging of electric quadrupole interactions and paramagnetic interactions, correspondingly ~30.6° and ~70.1°. In amorphous materials, residual line broadening remains since each segment is in a slightly different environment, therefore exhibiting a slightly different NMR frequency. Line broadening or splitting by dipolar or
J-coupling In nuclear chemistry and nuclear physics, ''J''-couplings (also called spin-spin coupling or indirect dipole–dipole coupling) are mediated through chemical bonds connecting two spins. It is an indirect interaction between two nuclear spins tha ...
s to nearby 1H nuclei is usually removed by radio-frequency pulses applied at the 1H frequency during signal detection. The concept of cross polarization developed by Sven Hartmann and Erwin Hahn was utilized in transferring magnetization from protons to less sensitive nuclei by M.G. Gibby, Alex Pines and John S. Waugh. Then, Jake Schaefer and Ed Stejskal demonstrated the powerful use of cross polarization under MAS conditions (CP-MAS) and proton decoupling, which is now routinely employed to measure high resolution spectra of low-abundance and low-sensitivity nuclei, such as carbon-13, silicon-29, or nitrogen-15, in solids. Significant further signal enhancement can be achieved by dynamic nuclear polarization from unpaired electrons to the nuclei, usually at temperatures near 110 K.


Sensitivity

Because the intensity of nuclear magnetic resonance signals and, hence, the sensitivity of the technique depends on the strength of the magnetic field, the technique has also advanced over the decades with the development of more powerful magnets. Advances made in audio-visual technology have also improved the signal-generation and processing capabilities of newer instruments. As noted above, the sensitivity of nuclear magnetic resonance signals is also dependent on the presence of a magnetically susceptible nuclide and, therefore, either on the natural abundance of such nuclides or on the ability of the experimentalist to artificially enrich the molecules, under study, with such nuclides. The most abundant naturally occurring isotopes of hydrogen and phosphorus (for example) are both magnetically susceptible and readily useful for nuclear magnetic resonance spectroscopy. In contrast, carbon and nitrogen have useful isotopes but which occur only in very low natural abundance. Other limitations on sensitivity arise from the quantum-mechanical nature of the phenomenon. For quantum states separated by energy equivalent to radio frequencies, thermal energy from the environment causes the populations of the states to be close to equal. Since incoming radiation is equally likely to cause stimulated emission (a transition from the upper to the lower state) as absorption, the NMR effect depends on an excess of nuclei in the lower states. Several factors can reduce sensitivity, including: * Increasing temperature, which evens out the Boltzmann population of states. Conversely, low temperature NMR can sometimes yield better results than room-temperature NMR, providing the sample remains liquid. * Saturation of the sample with energy applied at the resonant radiofrequency. This manifests in both CW and pulsed NMR; in the first case (CW) this happens by using too much continuous power that keeps the upper spin levels completely populated; in the second case (pulsed), each pulse (that is at least a 90° pulse) leaves the sample saturated, and four to five times the (longitudinal) relaxation time (5''T''1) must pass before the next pulse or pulse sequence can be applied. For single pulse experiments, shorter RF pulses that tip the magnetization by less than 90° can be used, which loses some intensity of the signal, but allows for shorter ''recycle delays''. The optimum there is called an ''Ernst angle'', after the Nobel laureate. Especially in solid state NMR, or in samples containing very few nuclei with spin (diamond with the natural 1% of carbon-13 is especially troublesome here) the longitudinal relaxation times can be on the range of hours, while for proton-NMR they are often in the range of one second. * Non-magnetic effects, such as electric-
quadrupole A quadrupole or quadrapole is one of a sequence of configurations of things like electric charge or current, or gravitational mass that can exist in ideal form, but it is usually just part of a multipole expansion of a more complex structure re ...
coupling of spin-1 and spin- nuclei with their local environment, which broaden and weaken absorption peaks. , an abundant spin-1 nucleus, is difficult to study for this reason. High resolution NMR instead probes molecules using the rarer isotope, which has spin-.


Isotopes

Many isotopes of chemical elements can be used for NMR analysis. Commonly used nuclei: * , the most commonly used spin- nucleus in NMR investigations, has been studied using many forms of NMR. Hydrogen is highly abundant, especially in biological systems. It is the nucleus providing the strongest NMR signal (apart from , which is not commonly used due to its instability and radioactivity).
Proton NMR Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the stru ...
has a narrow chemical-shift range but gives sharp signals in solution state. Fast acquisition of quantitative spectra (with peak integrals in stoichiometric ratios) is possible due to short relaxation time. The nucleus has provided the sole diagnostic signal for clinical
magnetic resonance imaging Magnetic resonance imaging (MRI) is a medical imaging technique used in radiology to generate pictures of the anatomy and the physiological processes inside the body. MRI scanners use strong magnetic fields, magnetic field gradients, and ...
(MRI). * , a spin-1 nucleus, is commonly utilized to provide a signal-free medium in the form of
deuterated solvents Deuterated solvents are a group of compounds where one or more hydrogen atoms are substituted by deuterium atoms. These isotopologues of common solvents are often used in nuclear magnetic resonance spectroscopy. Examples * Heavy water * Deuterat ...
for proton NMR, to avoid signal interference from hydrogen-containing solvents in measurement of NMR of solutes. It is also used in determining the behavior of lipids in lipid membranes and other solids or liquid crystals as it is a relatively non-perturbing label which can selectively replace . Alternatively, can be detected in media specially labeled with . Deuterium resonance is commonly used in high-resolution
NMR spectroscopy Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique based on re-orientation of atomic nuclei with non-zero nuclear spins in an external magnetic f ...
to monitor drift of the magnetic field strength (lock) and to monitor the homogeneity of the external magnetic field. * is very sensitive to NMR. It exists at a very low concentration in natural helium and can be purified from . It is used mainly in studies of endohedral fullerenes, where its chemical inertness is beneficial to ascertaining the structure of the entrapping fullerene. * is more sensitive than and yields sharper signals. The nuclear spin of 10B is 3 and that of 11B is . Quartz tubes must be used because
borosilicate Borosilicate glass is a type of glass with silicon dioxide, silica and boron trioxide as the main glass-forming constituents. Borosilicate glasses are known for having very low coefficient of thermal expansion, coefficients of thermal expansion ( ...
glass interferes with measurement. * , a spin- nucleus, is widely used, despite its relative paucity in naturally occurring carbon (approximately 1.1%). It is stable to nuclear decay. Since there is a low percentage in natural carbon, spectrum acquisition on samples which have not been enriched in takes a long time. Frequently used for labeling of compounds in synthetic and metabolic studies. Has low sensitivity and moderately wide chemical shift range, yields sharp signals. Low percentage makes it useful by preventing spin–spin couplings and makes the spectrum appear less crowded. Slow relaxation of 13C not bonded to hydrogen means that spectra are not integrable unless long acquisition times are used. * , spin-1, is a medium sensitivity nucleus with wide chemical shift range. Its large
quadrupole A quadrupole or quadrapole is one of a sequence of configurations of things like electric charge or current, or gravitational mass that can exist in ideal form, but it is usually just part of a multipole expansion of a more complex structure re ...
moment interferes with acquisition of high resolution spectra, limiting usefulness to smaller molecules and functional groups with a high degree of symmetry such as in the head-groups of lipids. * , spin-, is relatively commonly used. Can be used for isotopically labeling compounds. Very insensitive but yields sharp signals. Low percentage in natural nitrogen together with low sensitivity requires high concentrations or expensive isotope enrichment. * , spin-, low sensitivity and very low natural abundance (0.037%), wide chemical shift range (up to 2000 ppm). Its quadrupole moment causes line broadening. Used in metabolic and biochemical studies of chemical equilibria. * , spin-, relatively commonly measured. Sensitive, yields sharp signals, has a wide chemical shift range. * , spin-, 100% of natural phosphorus. Medium sensitivity, wide chemical shift range, yields sharp lines. Spectra tend to have a moderate level of noise. Used in biochemical studies and in coordination chemistry with phosphorus-containing ligands. * and , spin-, broad signal. is significantly more sensitive, preferred over despite its slightly broader signal. Organic chlorides yield very broad signals. Its use is limited to inorganic and ionic chlorides and very small organic molecules. * , spin-, relatively small quadrupole moment, moderately sensitive, very low natural abundance. Used in biochemistry to study calcium binding to DNA, proteins, etc. * , used in studies of
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
s and complexes. Other nuclei (usually used in the studies of their complexes and chemical bonding, or to detect presence of the element): * , * * * * * * * * * * , , * * , * , * * * * * * , * * , * * * * * * * * * * * * * * , * * *


Applications

NMR is extensively used in medicine in the form of
magnetic resonance imaging Magnetic resonance imaging (MRI) is a medical imaging technique used in radiology to generate pictures of the anatomy and the physiological processes inside the body. MRI scanners use strong magnetic fields, magnetic field gradients, and ...
. NMR is widely used in organic chemistry and industrially mainly for analysis of chemicals. The technique is also used to measure the ratio between water and fat in foods, monitor the flow of corrosive fluids in pipes, or to study molecular structures such as catalysts.


Medicine

The application of nuclear magnetic resonance best known to the general public is
magnetic resonance imaging Magnetic resonance imaging (MRI) is a medical imaging technique used in radiology to generate pictures of the anatomy and the physiological processes inside the body. MRI scanners use strong magnetic fields, magnetic field gradients, and ...
for medical diagnosis and magnetic resonance microscopy in research settings. However, it is also widely used in biochemical studies, notably in NMR spectroscopy such as
proton NMR Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the stru ...
,
carbon-13 NMR Carbon-13 (C13) nuclear magnetic resonance (most commonly known as carbon-13 NMR spectroscopy or 13C NMR spectroscopy or sometimes simply referred to as carbon NMR) is the application of nuclear magnetic resonance (NMR) spectroscopy to carbon. It ...
, deuterium NMR and phosphorus-31 NMR. Biochemical information can also be obtained from living tissue (e.g. human
brain The brain is an organ (biology), organ that serves as the center of the nervous system in all vertebrate and most invertebrate animals. It consists of nervous tissue and is typically located in the head (cephalization), usually near organs for ...
tumor A neoplasm () is a type of abnormal and excessive growth of tissue. The process that occurs to form or produce a neoplasm is called neoplasia. The growth of a neoplasm is uncoordinated with that of the normal surrounding tissue, and persists ...
s) with the technique known as in vivo magnetic resonance spectroscopy or
chemical shift In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of an atomic nucleus relative to a standard in a magnetic field. Often the position and number of chemical shifts are diagnostic of the structure of ...
NMR microscopy. These spectroscopic studies are possible because nuclei are surrounded by orbiting electrons, which are charged particles that generate small, local magnetic fields that add to or subtract from the external magnetic field, and so will partially shield the nuclei. The amount of shielding depends on the exact local environment. For example, a hydrogen bonded to an
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
will be shielded differently from a hydrogen bonded to a carbon atom. In addition, two hydrogen nuclei can interact via a process known as
spin–spin coupling In quantum mechanics, angular momentum coupling is the procedure of constructing eigenstates of total angular momentum out of eigenstates of separate angular momenta. For instance, the orbit and spin of a single particle can interact through spi ...
, if they are on the same molecule, which will split the lines of the spectra in a recognizable way. As one of the two major spectroscopic techniques used in
metabolomics Metabolomics is the scientific study of chemical processes involving metabolites, the small molecule substrates, intermediates, and products of cell metabolism. Specifically, metabolomics is the "systematic study of the unique chemical fingerpri ...
, NMR is used to generate metabolic fingerprints from biological fluids to obtain information about disease states or toxic insults.


Chemistry

The aforementioned
chemical shift In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of an atomic nucleus relative to a standard in a magnetic field. Often the position and number of chemical shifts are diagnostic of the structure of ...
came as a disappointment to physicists who had hoped that the resonance frequency of each nuclear species would be constant in a given magnetic field. But about 1951, chemist S. S. Dharmatti pioneered a way to determine the structure of many compounds by studying the peaks of nuclear magnetic resonance spectra. It can be a very selective technique, distinguishing among many atoms within a molecule or collection of molecules of very similar type but which differ only in terms of their local chemical environment. NMR spectroscopy is used to unambiguously identify known and novel compounds, and as such, is usually required by scientific journals for identity confirmation of synthesized new compounds. See the articles on
carbon-13 NMR Carbon-13 (C13) nuclear magnetic resonance (most commonly known as carbon-13 NMR spectroscopy or 13C NMR spectroscopy or sometimes simply referred to as carbon NMR) is the application of nuclear magnetic resonance (NMR) spectroscopy to carbon. It ...
and
proton NMR Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the stru ...
for detailed discussions. A chemist can determine the identity of a compound by comparing the observed nuclear precession frequencies to known or predicted frequencies. Further structural data can be elucidated by observing ''
spin–spin coupling In quantum mechanics, angular momentum coupling is the procedure of constructing eigenstates of total angular momentum out of eigenstates of separate angular momenta. For instance, the orbit and spin of a single particle can interact through spi ...
'', a process by which the precession frequency of a nucleus can be influenced by the spin orientation of a chemically bonded nucleus. Spin–spin coupling is easily observed in NMR of hydrogen-1 ( NMR) since its natural abundance is nearly 100%. Because the nuclear magnetic resonance ''timescale'' is rather slow, compared to other spectroscopic methods, changing the temperature of a ''T''2* experiment can also give information about fast reactions, such as the Cope rearrangement or about structural dynamics, such as ring-flipping in
cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colourless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...
. At low enough temperatures, a distinction can be made between the axial and equatorial hydrogens in cyclohexane. An example of nuclear magnetic resonance being used in the determination of a structure is that of
buckminsterfullerene Buckminsterfullerene is a type of fullerene with the formula . It has a cage-like fused-ring structure ( truncated icosahedron) made of twenty hexagons and twelve pentagons, and resembles a football. Each of its 60 carbon atoms is bonded to i ...
(often called "buckyballs", composition C60). This now famous form of carbon has 60 carbon atoms forming a sphere. The carbon atoms are all in identical environments and so should see the same internal H field. Unfortunately, buckminsterfullerene contains no hydrogen and so nuclear magnetic resonance has to be used. spectra require longer acquisition times since carbon-13 is not the common isotope of carbon (unlike hydrogen, where is the common isotope). However, in 1990 the spectrum was obtained by R. Taylor and co-workers at the
University of Sussex The University of Sussex is a public university, public research university, research university located in Falmer, East Sussex, England. It lies mostly within the city boundaries of Brighton and Hove. Its large campus site is surrounded by the ...
and was found to contain a single peak, confirming the unusual structure of buckminsterfullerene.


Battery

Nuclear Magnetic Resonance (NMR) is a powerful analytical tool for investigating the local structure and ion dynamics in battery materials. NMR provides unique insights into the short-range atomic environments within complex electrochemical systems such as batteries. Electrochemical processes rely on redox reactions, in which 7Li or 23Na are often involved. Accordingly, their NMR spectroscopies are affected by the electronic structure of the material, which makes NMR an essential technique for probing the behavior of battery components during operation. Some of the applications of NMR in battery research include: *Electrodes and Structural Transformations: During charge and discharge cycles, the materials in the anodes and cathodes undergo local structural transformations. These changes can be monitored using NMR by analyzing the signal's line shape, line intensity, and chemical shift. These transformations are often not captured by
X-ray diffraction X-ray diffraction is a generic term for phenomena associated with changes in the direction of X-ray beams due to interactions with the electrons around atoms. It occurs due to elastic scattering, when there is no change in the energy of the waves. ...
techniques (providing long-range information), making NMR indispensable for understanding the underlying mechanisms of energy storage. *Metal Dendrite Formation: One of the challenges in lithium and sodium-based batteries is the formation of metal dendrites, which can lead to short circuits and catastrophic battery failure. In Situ NMR allows researchers to observe the formation of lithium or sodium dendrites in real time during battery cycling. Varying the cycling rates can also quantify the effect on dendrite formation, aiding in the development of strategies to suppress dendrite growth and reduce the risk of short circuits. * Solid Electrolytes and Interfaces: Solid electrolytes, a key focus of next-generation battery research, often suffer from limited ion diffusion rates. NMR techniques can measure diffusivity in solid electrolytes, helping researchers understand how to enhance ion conductivity. Furthermore, NMR is used to study the Solid Electrolyte Interface (SEI), a layer that forms on the electrode surface and thus influences battery stability.
Solid-state NMR Solid-state nuclear magnetic resonance (ssNMR) is a spectroscopy technique used to characterize atomic-level structure and dynamics in solid materials. ssNMR spectra are broader due to nuclear spin interactions which can be categorized as dipolar ...
(ssNMR) is particularly valuable for characterizing the composition and ion dynamics within the SEI layer due to its nondestructive testing capabilities. ''In Situ'' and ''Ex Situ'' NMR Techniques
NMR technology can be divided into two main experimental approaches in battery research: ''In Situ'' NMR and ''Ex Situ'' NMR. Each offers unique advantages depending on the research goals. *''In Situ'' NMR: ''In situ'' NMR enables real-time observation of chemical and structural changes in batteries while they are operating. This is particularly important for studying transient species that only exist under working conditions, such as certain intermediate reaction products. ''In situ'' NMR has become a critical tool for understanding processes like lithium and sodium plating and dendrite formation during battery cycling.
*''Ex Situ'' NMR: ''Ex situ'' NMR is used after the battery has been disassembled, allowing for high-resolution analysis of battery components. It is often employed to study a wide range of nuclei, including 1H, 2H, 6Li, 7Li, 13C, 15N, 17O, 19F, 25Mg, 29Si, 31P, 51V, 133Cs. Many of these nuclei are quadrupolar or present in low abundance, making them difficult to detect. However, ''ex situ'' NMR benefits from better sensitivity and narrower linewidths, which can be further improved by employing larger sample volumes, higher magnetic fields, or
magic angle spinning In solid-state NMR spectroscopy, magic-angle spinning (MAS) is a technique routinely used to produce better resolution NMR spectra. MAS NMR consists in spinning the sample (usually at a frequency of 1 to 130  kHz) at the magic angle θm (ca ...
(MAS).


Purity determination (w/w NMR)

While NMR is primarily used for structural determination, it can also be used for purity determination, provided that the structure and
molecular weight A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of the compound is known. This technique requires the use of an internal standard of known purity. Typically this standard will have a high molecular weight to facilitate accurate weighing, but relatively few protons so as to give a clear peak for later integration e.g. 1,2,4,5-tetrachloro-3-nitrobenzene. Accurately weighed portions of the standard and sample are combined and analysed by NMR. Suitable peaks from both compounds are selected and the purity of the sample is determined via the following equation. :\mathrm = \frac \times P Where: * ''w''std: weight of internal standard * ''w''spl: weight of sample * ''n'' sub>std: the integrated area of the peak selected for comparison in the standard, corrected for the number of protons in that
functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...
* ''n'' sub>spl: the integrated area of the peak selected for comparison in the sample, corrected for the number of protons in that
functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...
* ''MW''std:
molecular weight A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of standard * ''MW''spl:
molecular weight A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of sample * ''P'': purity of internal standard


Non-destructive testing

Nuclear magnetic resonance is extremely useful for analyzing samples non-destructively. Radio-frequency magnetic fields easily penetrate many types of matter and anything that is not highly conductive or inherently
ferromagnetic Ferromagnetism is a property of certain materials (such as iron) that results in a significant, observable magnetic permeability, and in many cases, a significant magnetic coercivity, allowing the material to form a permanent magnet. Ferromagne ...
. For example, various expensive biological samples, such as
nucleic acids Nucleic acids are large biomolecules that are crucial in all cells and viruses. They are composed of nucleotides, which are the monomer components: a 5-carbon sugar, a phosphate group and a nitrogenous base. The two main classes of nucleic a ...
, including
RNA Ribonucleic acid (RNA) is a polymeric molecule that is essential for most biological functions, either by performing the function itself (non-coding RNA) or by forming a template for the production of proteins (messenger RNA). RNA and deoxyrib ...
and
DNA Deoxyribonucleic acid (; DNA) is a polymer composed of two polynucleotide chains that coil around each other to form a double helix. The polymer carries genetic instructions for the development, functioning, growth and reproduction of al ...
, or
protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residue (biochemistry), residues. Proteins perform a vast array of functions within organisms, including Enzyme catalysis, catalysing metab ...
s, can be studied using nuclear magnetic resonance for weeks or months before using destructive biochemical experiments. This also makes nuclear magnetic resonance a good choice for analyzing dangerous samples.


Segmental and molecular motions

In addition to providing static information on molecules by determining their 3D structures, one of the remarkable advantages of NMR over
X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...
is that it can be used to obtain important dynamic information. This is due to the orientation dependence of the chemical-shift, dipole-coupling, or electric-quadrupole-coupling contributions to the instantaneous NMR frequency in an anisotropic molecular environment. When the molecule or segment containing the NMR-observed nucleus changes its orientation relative to the external field, the NMR frequency changes, which can result in changes in one- or two-dimensional spectra or in the relaxation times, depending on the correlation time and amplitude of the motion.


Data acquisition in the petroleum industry

Another use for nuclear magnetic resonance is
data acquisition Data acquisition is the process of sampling signals that measure real-world physical conditions and converting the resulting samples into digital numeric values that can be manipulated by a computer. Data acquisition systems, abbreviated by the ...
in the
petroleum industry The petroleum industry, also known as the oil industry, includes the global processes of hydrocarbon exploration, exploration, extraction of petroleum, extraction, oil refinery, refining, Petroleum transport, transportation (often by oil tankers ...
for
petroleum Petroleum, also known as crude oil or simply oil, is a naturally occurring, yellowish-black liquid chemical mixture found in geological formations, consisting mainly of hydrocarbons. The term ''petroleum'' refers both to naturally occurring un ...
and
natural gas Natural gas (also fossil gas, methane gas, and gas) is a naturally occurring compound of gaseous hydrocarbons, primarily methane (95%), small amounts of higher alkanes, and traces of carbon dioxide and nitrogen, hydrogen sulfide and helium ...
exploration and recovery. Initial research in this domain began in the 1950s, however, the first commercial instruments were not released until the early 1990s. A
borehole A borehole is a narrow shaft bored in the ground, either vertically or horizontally. A borehole may be constructed for many different purposes, including the extraction of water ( drilled water well and tube well), other liquids (such as petr ...
is drilled into rock and sedimentary strata into which nuclear magnetic resonance logging equipment is lowered. Nuclear magnetic resonance analysis of these boreholes is used to measure rock porosity, estimate permeability from pore size distribution and identify pore fluids (water, oil and gas). These instruments are typically low field NMR spectrometers. NMR logging, a subcategory of electromagnetic logging, measures the induced magnet moment of hydrogen nuclei (protons) contained within the fluid-filled pore space of porous media (reservoir rocks). Unlike conventional logging measurements (e.g., acoustic, density, neutron, and resistivity), which respond to both the rock matrix and fluid properties and are strongly dependent on mineralogy, NMR-logging measurements respond to the presence of hydrogen. Because hydrogen atoms primarily occur in pore fluids, NMR effectively responds to the volume, composition, viscosity, and distribution of these fluids, for example oil, gas or water. NMR logs provide information about the quantities of fluids present, the properties of these fluids, and the sizes of the pores containing these fluids. From this information, it is possible to infer or estimate: * The volume (porosity) and distribution (permeability) of the rock pore space * Rock composition * Type and quantity of fluid hydrocarbons * Hydrocarbon producibility The basic core and log measurement is the ''T''2 decay, presented as a distribution of ''T''2 amplitudes versus time at each sample depth, typically from 0.3 ms to 3 s. The ''T''2 decay is further processed to give the total pore volume (the total porosity) and pore volumes within different ranges of ''T''2. The most common volumes are the bound fluid and free fluid. A permeability estimate is made using a transform such as the Timur-Coates or SDR permeability transforms. By running the log with different acquisition parameters, direct hydrocarbon typing and enhanced diffusion are possible.


Flow probes for NMR spectroscopy

Real-time applications of NMR in liquid media have been developed using specifically designed flow probes (flow cell assemblies) which can replace standard tube probes. This has enabled techniques that can incorporate the use of
high performance liquid chromatography High-performance liquid chromatography (HPLC), formerly referred to as high-pressure liquid chromatography, is a technique in analytical chemistry used to separate, identify, and quantify specific components in mixtures. The mixtures can origina ...
(HPLC) or other continuous flow sample introduction devices. These flow probes have used in various online process monitoring such as chemical reactions, environmental pollutant degradation.


Process control

NMR has now entered the arena of real-time
process control Industrial process control (IPC) or simply process control is a system used in modern manufacturing which uses the principles of control theory and physical industrial control systems to monitor, control and optimize continuous Industrial processe ...
and
process optimization Process optimization is the discipline of adjusting a process so as to make the best or most effective use of some specified set of parameters without violating some constraint. Common goals are minimizing cost and maximizing throughput and/or e ...
in
oil refineries An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefied pet ...
and
petrochemical Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable s ...
plants. Two different types of NMR analysis are utilized to provide real time analysis of feeds and products in order to control and optimize unit operations. Time-domain NMR (TD-NMR) spectrometers operating at low field (2–20 MHz for ) yield free induction decay data that can be used to determine absolute
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
content values, rheological information, and component composition. These spectrometers are used in
mining Mining is the Resource extraction, extraction of valuable geological materials and minerals from the surface of the Earth. Mining is required to obtain most materials that cannot be grown through agriculture, agricultural processes, or feasib ...
,
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
production,
cosmetics Cosmetics are substances that are intended for application to the body for cleansing, beautifying, promoting attractiveness, or altering appearance. They are mixtures of chemical compounds derived from either Natural product, natural source ...
and food manufacturing as well as
coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other Chemical element, elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal i ...
analysis. High resolution FT-NMR spectrometers operating in the 60 MHz range with shielded permanent magnet systems yield high resolution NMR spectra of
refinery A refinery is a production facility composed of a group of chemical engineering unit processes and unit operations refining certain materials or converting raw material into products of value. Types of refineries Different types of refineries ...
and
petrochemical Petrochemicals (sometimes abbreviated as petchems) are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable s ...
streams. The variation observed in these spectra with changing physical and chemical properties is modeled using
chemometrics Chemometrics is the science of extracting information from chemical systems by data-driven means. Chemometrics is inherently interdisciplinary, using methods frequently employed in core data-analytic disciplines such as multivariate statistics, ap ...
to yield predictions on unknown samples. The prediction results are provided to
control systems A control system manages, commands, directs, or regulates the behavior of other devices or systems using control loops. It can range from a single home heating controller using a thermostat controlling a domestic boiler to large industrial co ...
via analogue or digital outputs from the spectrometer.


Earth's field NMR

In the
Earth's magnetic field Earth's magnetic field, also known as the geomagnetic field, is the magnetic field that extends from structure of Earth, Earth's interior out into space, where it interacts with the solar wind, a stream of charged particles emanating from ...
, NMR frequencies are in the
audio frequency An audio frequency or audible frequency (AF) is a periodic vibration whose frequency is audible to the average human. The SI unit of frequency is the hertz (Hz). It is the property of sound that most determines pitch. The generally accepted ...
range, or the
very low frequency Very low frequency or VLF is the ITU designation for radio frequencies (RF) in the range of 3–30  kHz, corresponding to wavelengths from 100 to 10 km, respectively. The band is also known as the myriameter band or myriameter wave ...
and
ultra low frequency Ultra low frequency (ULF) is the ITU designation for the frequency range of electromagnetic waves between 300 hertz and 3 kilohertz, corresponding to wavelengths between 1,000 and 100 km. In magnetosphere science and seismology, alternative ...
bands of the
radio frequency Radio frequency (RF) is the oscillation rate of an alternating electric current or voltage or of a magnetic, electric or electromagnetic field or mechanical system in the frequency range from around to around . This is roughly between the u ...
spectrum. Earth's field NMR (EFNMR) is typically stimulated by applying a relatively strong dc magnetic field pulse to the sample and, after the end of the pulse, analyzing the resulting low frequency alternating magnetic field that occurs in the Earth's magnetic field due to free induction decay (FID). These effects are exploited in some types of
magnetometer A magnetometer is a device that measures magnetic field or magnetic dipole moment. Different types of magnetometers measure the direction, strength, or relative change of a magnetic field at a particular location. A compass is one such device, ...
s, EFNMR spectrometers, and MRI imagers. Their inexpensive portable nature makes these instruments valuable for field use and for teaching the principles of NMR and MRI. An important feature of EFNMR spectrometry compared with high-field NMR is that some aspects of molecular structure can be observed more clearly at low fields and low frequencies, whereas other aspects observable at high fields are not observable at low fields. This is because: * Electron-mediated heteronuclear ''J''-couplings (
spin–spin coupling In quantum mechanics, angular momentum coupling is the procedure of constructing eigenstates of total angular momentum out of eigenstates of separate angular momenta. For instance, the orbit and spin of a single particle can interact through spi ...
s) are field independent, producing clusters of two or more frequencies separated by several Hz, which are more easily observed in a fundamental resonance of about 2 kHz."Indeed it appears that enhanced resolution is possible due to the long spin relaxation times and high field homogeneity which prevail in EFNMR." * Chemical shifts of several ppm are clearly separated in high field NMR spectra, but have separations of only a few millihertz at proton EFNMR frequencies, so are usually not resolved.


Zero field NMR

In zero field NMR all magnetic fields are shielded such that magnetic fields below 1 nT (nano tesla) are achieved and the nuclear precession frequencies of all nuclei are close to zero and indistinguishable. Under those circumstances the observed spectra are no-longer dictated by chemical shifts but primarily by ''J''-coupling interactions which are independent of the external magnetic field. Since inductive detection schemes are not sensitive at very low frequencies, on the order of the ''J''-couplings (typically between 0 and 1000 Hz), alternative detection schemes are used. Specifically, sensitive
magnetometer A magnetometer is a device that measures magnetic field or magnetic dipole moment. Different types of magnetometers measure the direction, strength, or relative change of a magnetic field at a particular location. A compass is one such device, ...
s turn out to be good detectors for zero field NMR. A zero magnetic field environment does not provide any polarization hence it is the combination of zero field NMR with hyperpolarization schemes that makes zero field NMR desirable.


Quantum computing

NMR
quantum computing A quantum computer is a computer that exploits quantum mechanical phenomena. On small scales, physical matter exhibits properties of wave-particle duality, both particles and waves, and quantum computing takes advantage of this behavior using s ...
uses the
spin Spin or spinning most often refers to: * Spin (physics) or particle spin, a fundamental property of elementary particles * Spin quantum number, a number which defines the value of a particle's spin * Spinning (textiles), the creation of yarn or thr ...
states of nuclei within molecules as
qubit In quantum computing, a qubit () or quantum bit is a basic unit of quantum information—the quantum version of the classic binary bit physically realized with a two-state device. A qubit is a two-state (or two-level) quantum-mechanical syste ...
s. NMR differs from other implementations of quantum computers in that it uses an ensemble of systems; in this case, molecules.


Magnetometers

Various magnetometers use NMR effects to measure magnetic fields, including proton precession magnetometers (PPM) (also known as
proton magnetometer A proton magnetometer, also known as a proton precession magnetometer (PPM), uses the principle of Earth's field NMR, Earth's field nuclear magnetic resonance (EFNMR) to measure very small variations in the Earth's magnetic field, allowing ferrou ...
s), and Overhauser magnetometers.


SNMR

Surface magnetic resonance (or magnetic resonance sounding) is based on the principle of nuclear magnetic resonance (NMR) and measurements can be used to indirectly estimate the water content of saturated and unsaturated zones in the earth's subsurface. SNMR is used to estimate aquifer properties, including quantity of water contained in the
aquifer An aquifer is an underground layer of water-bearing material, consisting of permeability (Earth sciences), permeable or fractured rock, or of unconsolidated materials (gravel, sand, or silt). Aquifers vary greatly in their characteristics. The s ...
,
porosity Porosity or void fraction is a measure of the void (i.e. "empty") spaces in a material, and is a fraction of the volume of voids over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Strictly speaking, some tests measure ...
, and
hydraulic conductivity In science and engineering, hydraulic conductivity (, in SI units of meters per second), is a property of porous materials, soils and Rock (geology), rocks, that describes the ease with which a fluid (usually water) can move through the porosity, ...
.


Makers of NMR equipment

Major NMR instrument makers include *
Thermo Fisher Scientific Thermo Fisher Scientific Inc. is an American life science and clinical research company. It is a global supplier of analytical instruments, clinical development solutions, specialty diagnostics, laboratory, pharmaceutical and biotechnology s ...
* Magritek *
Oxford Instruments Oxford Instruments plc is a United Kingdom manufacturing and research company that designs and manufactures tools and systems for industry and research. The company is headquartered in Abingdon, Oxfordshire, England, with sites in the United Ki ...
*
Bruker Bruker Corporation is an American manufacturer of scientific instruments for molecular and materials research, as well as for industrial and applied analysis. It is headquartered in Billerica, Massachusetts, and is the publicly traded parent comp ...
* Spinlock SRL *
General Electric General Electric Company (GE) was an American Multinational corporation, multinational Conglomerate (company), conglomerate founded in 1892, incorporated in the New York (state), state of New York and headquartered in Boston. Over the year ...
*
JEOL is a major developer and manufacturer of electron microscopes and other scientific instruments, industrial equipment and medical equipment. Its headquarters are in Tokyo, Japan, with 25 domestic and foreign subsidiaries and associated companies ...
* Kimble Chase *
Philips Koninklijke Philips N.V. (), simply branded Philips, is a Dutch multinational health technology company that was founded in Eindhoven in 1891. Since 1997, its world headquarters have been situated in Amsterdam, though the Benelux headquarter ...
*
Siemens AG Siemens AG ( ) is a German multinational technology conglomerate. It is focused on industrial automation, building automation, rail transport and health technology. Siemens is the largest engineering company in Europe, and holds the posit ...
*
Agilent Technologies Agilent Technologies, Inc. is an American global company headquartered in Santa Clara, California, that provides instruments, software, services, and consumables for laboratories. Agilent was established in 1999 as a spin-off from Hewlett-Packar ...
(who acquired Varian, Inc.).


See also

* Benchtop NMR spectrometer * Larmor equation (Not to be confused with
Larmor formula In electrodynamics, the Larmor formula is used to calculate the total power radiated by a nonrelativistic point charge as it accelerates. It was first derived by J. J. Larmor in 1897, in the context of the wave theory of light. When any charge ...
). *
Least-squares spectral analysis Least-squares spectral analysis (LSSA) is a method of estimating a Spectral density estimation#Overview, frequency spectrum based on a least-squares fit of Sine wave, sinusoids to data samples, similar to Fourier analysis. Fourier analysis, the ...
*
Liquid nitrogen Liquid nitrogen (LN2) is nitrogen in a liquid state at cryogenics, low temperature. Liquid nitrogen has a boiling point of about . It is produced industrially by fractional distillation of liquid air. It is a colorless, mobile liquid whose vis ...
* NMR crystallography *
NMR spectra database A nuclear magnetic resonance spectra database is an electronic repository of information concerning Nuclear magnetic resonance (NMR) spectra. Such repositories can be downloaded as self-contained data sets or used online. The form in which the ...
* Nuclear magnetic resonance in porous media *
Nuclear quadrupole resonance Nuclear quadrupole resonance spectroscopy or NQR is a chemical analysis technique related to nuclear magnetic resonance (NMR). Unlike NMR, NQR transitions of nuclei can be detected in the absence of a magnetic field, and for this reason NQR spectro ...
(NQR) *
Protein dynamics In molecular biology, proteins are generally thought to adopt unique structures determined by their amino acid sequences. However, proteins are not strictly static objects, but rather populate ensembles of (sometimes similar) conformations. Tran ...
*
Rabi cycle In physics, the Rabi cycle (or Rabi flop) is the cyclic behaviour of a two-level quantum system in the presence of an oscillatory driving field. A great variety of physical processes belonging to the areas of quantum computing, condensed matter, ...
* Relaxometry *
Spin echo In magnetic resonance, a spin echo or Hahn echo is the refocusing of spin magnetisation by a pulse of resonant electromagnetic radiation. Modern nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) make use of this effect. The ...
* Structure-based assignment


References


Further reading

* * * K.V.R. Chary, Girjesh Govil (2008) ''NMR in Biological Systems: From Molecules to Human.'' Springer. . * *
The Feynman Lectures on Physics Vol. II Ch. 35: Paramagnetism and Magnetic Resonance
* * * * * * * * * *


External links


Tutorial





NMR Concepts
NMR Course Notes



Animations and simulations




Interactive simulation on the Bloch sphere


Video


introduction to NMR and MRI

Richard Ernst, NL – Developer of multidimensional NMR techniques
Freeview video provided by the Vega Science Trust.
'An Interview with Kurt Wuthrich'
Freeview video by the Vega Science Trust (Wüthrich was awarded a Nobel Prize in Chemistry in 2002 "for his development of nuclear magnetic resonance spectroscopy for determining the three-dimensional structure of biological macromolecules in solution").
The Nobel Prize Winner - Documentary about Richard R. Ernst
by Lukas Schwarzenbacher and Susanne Schmid (Swiss German with English subtitles) ; Other *
Spotlight on nuclear magnetic resonance: a timeless technique
{{DEFAULTSORT:Nuclear Magnetic Resonance Scientific techniques Articles containing video clips Biomagnetics