Paramagnetism

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When liquid oxygen is poured from a beaker into a strong magnet, the oxygen is temporarily contained between the magnetic poles owing to its paramagnetism. Liquid oxygen in a magnet.jpg
When liquid oxygen is poured from a beaker into a strong magnet, the oxygen is temporarily contained between the magnetic poles owing to its paramagnetism.

Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, diamagnetic materials are repelled by magnetic fields and form induced magnetic fields in the direction opposite to that of the applied magnetic field. [1] Paramagnetic materials include most chemical elements and some compounds; [2] they have a relative magnetic permeability slightly greater than 1 (i.e., a small positive magnetic susceptibility) and hence are attracted to magnetic fields. The magnetic moment induced by the applied field is linear in the field strength and rather weak. It typically requires a sensitive analytical balance to detect the effect and modern measurements on paramagnetic materials are often conducted with a SQUID magnetometer.

Magnetism class of physical phenomena

Magnetism is a class of physical phenomena that are mediated by magnetic fields. Electric currents and the magnetic moments of elementary particles give rise to a magnetic field, which acts on other currents and magnetic moments. The most familiar effects occur in ferromagnetic materials, which are strongly attracted by magnetic fields and can be magnetized to become permanent magnets, producing magnetic fields themselves. Only a few substances are ferromagnetic; the most common ones are iron, cobalt and nickel and their alloys. The prefix ferro- refers to iron, because permanent magnetism was first observed in lodestone, a form of natural iron ore called magnetite, Fe3O4.

Magnetic field Spatial distribution of vectors allowing the calculation of the magnetic force on a test particle

A magnetic field is a vector field that describes the magnetic influence of electric charges in relative motion and magnetized materials. The effects of magnetic fields are commonly seen in permanent magnets, which pull on magnetic materials and attract or repel other magnets. Magnetic fields surround and are created by magnetized material and by moving electric charges such as those used in electromagnets. They exert forces on nearby moving electrical charges and torques on nearby magnets. In addition, a magnetic field that varies with location exerts a force on magnetic materials. Both the strength and direction of a magnetic field vary with location. As such, it is described mathematically as a vector field.

Magnetization physical quantity, density of magnetic moment per unit volume

In classical electromagnetism, magnetization or magnetic polarization is the vector field that expresses the density of permanent or induced magnetic dipole moments in a magnetic material. The origin of the magnetic moments responsible for magnetization can be either microscopic electric currents resulting from the motion of electrons in atoms, or the spin of the electrons or the nuclei. Net magnetization results from the response of a material to an external magnetic field. Paramagnetic materials have a weak induced magnetization in a magnetic field, which disappears when the magnetic field is removed. Ferromagnetic and ferrimagnetic materials have strong magnetization in a magnetic field, and can be magnetized to have magnetization in the absence of an external field, becoming a permanent magnet. Magnetization is not necessarily uniform within a material, but may vary between different points. Magnetization also describes how a material responds to an applied magnetic field as well as the way the material changes the magnetic field, and can be used to calculate the forces that result from those interactions. It can be compared to electric polarization, which is the measure of the corresponding response of a material to an electric field in electrostatics. Physicists and engineers usually define magnetization as the quantity of magnetic moment per unit volume. It is represented by a pseudovector M.

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Paramagnetism is due to the presence of unpaired electrons in the material, so most atoms with incompletely filled atomic orbitals are paramagnetic, although exceptions such as copper exist. Due to their spin, unpaired electrons have a magnetic dipole moment and act like tiny magnets. An external magnetic field causes the electrons' spins to align parallel to the field, causing a net attraction. Paramagnetic materials include aluminium, oxygen, titanium, and iron oxide (FeO).

Unpaired electron electron that occupies an orbital of an atom singly

In chemistry, an unpaired electron is an electron that occupies an orbital of an atom singly, rather than as part of an electron pair. Each atomic orbital of an atom has a capacity to contain two electrons with opposite spins. As the formation of electron pairs is often energetically favourable, either in the form of a chemical bond or as a lone pair, unpaired electrons are relatively uncommon in chemistry, because an entity that carries an unpaired electron is usually rather reactive. In organic chemistry they typically only occur briefly during a reaction on an entity called a radical; however, they play an important role in explaining reaction pathways.

Atomic orbital A wave function for one electron in an atom having certain n and ℓ quantum numbers

In atomic theory and quantum mechanics, an atomic orbital is a mathematical function that describes the wave-like behavior of either one electron or a pair of electrons in an atom. This function can be used to calculate the probability of finding any electron of an atom in any specific region around the atom's nucleus. The term atomic orbital may also refer to the physical region or space where the electron can be calculated to be present, as defined by the particular mathematical form of the orbital.

Spin (physics) intrinsic form of angular momentum as a property of quantum particles

In quantum mechanics and particle physics, spin is an intrinsic form of angular momentum carried by elementary particles, composite particles (hadrons), and atomic nuclei.

Unlike ferromagnets, paramagnets do not retain any magnetization in the absence of an externally applied magnetic field because thermal motion randomizes the spin orientations. (Some paramagnetic materials retain spin disorder even at absolute zero, meaning they are paramagnetic in the ground state, i.e. in the absence of thermal motion.) Thus the total magnetization drops to zero when the applied field is removed. Even in the presence of the field there is only a small induced magnetization because only a small fraction of the spins will be oriented by the field. This fraction is proportional to the field strength and this explains the linear dependency. The attraction experienced by ferromagnetic materials is non-linear and much stronger, so that it is easily observed, for instance, in the attraction between a refrigerator magnet and the iron of the refrigerator itself.

Ferromagnetism physical phenomenon

Ferromagnetism is the basic mechanism by which certain materials form permanent magnets, or are attracted to magnets. In physics, several different types of magnetism are distinguished. Ferromagnetism is the strongest type and is responsible for the common phenomenon of magnetism in magnets encountered in everyday life. Substances respond weakly to magnetic fields with three other types of magnetism—paramagnetism, diamagnetism, and antiferromagnetism—but the forces are usually so weak that they can only be detected by sensitive instruments in a laboratory. An everyday example of ferromagnetism is a refrigerator magnet used to hold notes on a refrigerator door. The attraction between a magnet and ferromagnetic material is "the quality of magnetism first apparent to the ancient world, and to us today".

Absolute zero coldest possible temperature

Absolute zero is the lowest limit of the thermodynamic temperature scale, a state at which the enthalpy and entropy of a cooled ideal gas reach their minimum value, taken as 0°. The fundamental particles of nature have minimum vibrational motion, retaining only quantum mechanical, zero-point energy-induced particle motion. The theoretical temperature is determined by extrapolating the ideal gas law; by international agreement, absolute zero is taken as −273.15° on the Celsius scale, which equals −459.67° on the Fahrenheit scale. The corresponding Kelvin and Rankine temperature scales set their zero points at absolute zero by definition.

Ground state lowest energy state of quantum-mechanical system

The ground state of a quantum-mechanical system is its lowest-energy state; 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. In the quantum field theory, the ground state is usually called the vacuum state or the vacuum.

Relation to electron spins

Constituent atoms or molecules of paramagnetic materials have permanent magnetic moments (dipoles), even in the absence of an applied field. The permanent moment generally is due to the spin of unpaired electrons in atomic or molecular electron orbitals (see Magnetic moment). In pure paramagnetism, the dipoles do not interact with one another and are randomly oriented in the absence of an external field due to thermal agitation, resulting in zero net magnetic moment. When a magnetic field is applied, the dipoles will tend to align with the applied field, resulting in a net magnetic moment in the direction of the applied field. In the classical description, this alignment can be understood to occur due to a torque being provided on the magnetic moments by an applied field, which tries to align the dipoles parallel to the applied field. However, the true origins of the alignment can only be understood via the quantum-mechanical properties of spin and angular momentum.

Dipole Electromagnetic phenomenon

In electromagnetism, there are two kinds of dipoles:

Molecular orbital energy level in a molecule

In chemistry, a molecular orbital (MO) is a mathematical function describing the wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The term orbital was introduced by Robert S. Mulliken in 1932 as an abbreviation for one-electron orbital wave function. At an elementary level, it is used to describe the region of space in which the function has a significant amplitude. Molecular orbitals are usually constructed by combining atomic orbitals or hybrid orbitals from each atom of the molecule, or other molecular orbitals from groups of atoms. They can be quantitatively calculated using the Hartree–Fock or self-consistent field (SCF) methods.

Magnetic moment extensive physical property

The magnetic moment is the magnetic strength and orientation of a magnet or other object that produces a magnetic field. Examples of objects that have magnetic moments include: loops of electric current, permanent magnets, elementary particles, various molecules, and many astronomical objects.

If there is sufficient energy exchange between neighbouring dipoles, they will interact, and may spontaneously align or anti-align and form magnetic domains, resulting in ferromagnetism (permanent magnets) or antiferromagnetism, respectively. Paramagnetic behavior can also be observed in ferromagnetic materials that are above their Curie temperature, and in antiferromagnets above their Néel temperature. At these temperatures, the available thermal energy simply overcomes the interaction energy between the spins.

Antiferromagnetism magnetic ordering

In materials that exhibit antiferromagnetism, the magnetic moments of atoms or molecules, usually related to the spins of electrons, align in a regular pattern with neighboring spins pointing in opposite directions. This is, like ferromagnetism and ferrimagnetism, a manifestation of ordered magnetism.

Curie temperature Temperature below which magnetic properties change

In physics and materials science, the Curie temperature (TC), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can be replaced by induced magnetism. The Curie temperature is named after Pierre Curie, who showed that magnetism was lost at a critical temperature.

The Néel temperature or magnetic ordering temperature, TN, is the temperature above which an antiferromagnetic material becomes paramagnetic—that is, the thermal energy becomes large enough to destroy the microscopic magnetic ordering within the material.

In general, paramagnetic effects are quite small: the magnetic susceptibility is of the order of 10−3 to 10−5 for most paramagnets, but may be as high as 10−1 for synthetic paramagnets such as ferrofluids.

In electromagnetism, the magnetic susceptibility is a measure of how much a material will become magnetized in an applied magnetic field. Mathematically, it is the ratio of magnetization M to the applied magnetizing field intensity H. This allows a simple classification of most materials' response to an applied magnetic field into two categories: an alignment with the magnetic field, χ>0, called paramagnetism, or an alignment against the field, χ<0, called diamagnetism.

Ferrofluid

A ferrofluid or ferromagnetic fluid is a liquid that becomes strongly magnetized in the presence of a magnetic field.

Delocalization

Selected Pauli-paramagnetic metals [3]
MaterialMagnetic susceptibility, [10−5]

(SI units)

Tungsten 6.8
Caesium 5.1
Aluminium 2.2
Lithium 1.4
Magnesium 1.2
Sodium 0.72

In conductive materials, the electrons are delocalized, that is, they travel through the solid more or less as free electrons. Conductivity can be understood in a band structure picture as arising from the incomplete filling of energy bands. In an ordinary nonmagnetic conductor the conduction band is identical for both spin-up and spin-down electrons. When a magnetic field is applied, the conduction band splits apart into a spin-up and a spin-down band due to the difference in magnetic potential energy for spin-up and spin-down electrons. Since the Fermi level must be identical for both bands, this means that there will be a small surplus of the type of spin in the band that moved downwards. This effect is a weak form of paramagnetism known as Pauli paramagnetism.

The effect always competes with a diamagnetic response of opposite sign due to all the core electrons of the atoms. Stronger forms of magnetism usually require localized rather than itinerant electrons. However, in some cases a band structure can result in which there are two delocalized sub-bands with states of opposite spins that have different energies. If one subband is preferentially filled over the other, one can have itinerant ferromagnetic order. This situation usually only occurs in relatively narrow (d-)bands, which are poorly delocalized.

s and p electrons

Generally, strong delocalization in a solid due to large overlap with neighboring wave functions means that there will be a large Fermi velocity; this means that the number of electrons in a band is less sensitive to shifts in that band's energy, implying a weak magnetism. This is why s- and p-type metals are typically either Pauli-paramagnetic or as in the case of gold even diamagnetic. In the latter case the diamagnetic contribution from the closed shell inner electrons simply wins over the weak paramagnetic term of the almost free electrons.

d and f electrons

Stronger magnetic effects are typically only observed when d or f electrons are involved. Particularly the latter are usually strongly localized. Moreover, the size of the magnetic moment on a lanthanide atom can be quite large as it can carry up to 7 unpaired electrons in the case of gadolinium(III) (hence its use in MRI). The high magnetic moments associated with lanthanides is one reason why superstrong magnets are typically based on elements like neodymium or samarium.

Molecular localization

The above picture is a generalization as it pertains to materials with an extended lattice rather than a molecular structure. Molecular structure can also lead to localization of electrons. Although there are usually energetic reasons why a molecular structure results such that it does not exhibit partly filled orbitals (i.e. unpaired spins), some non-closed shell moieties do occur in nature. Molecular oxygen is a good example. Even in the frozen solid it contains di-radical molecules resulting in paramagnetic behavior. The unpaired spins reside in orbitals derived from oxygen p wave functions, but the overlap is limited to the one neighbor in the O2 molecules. The distances to other oxygen atoms in the lattice remain too large to lead to delocalization and the magnetic moments remain unpaired.

Theory

The Bohr–van Leeuwen theorem proves that there cannot be any diamagnetism or paramagnetism in a purely classical system. The paramagnetic response has then two possible quantum origins, either coming from permanent magnetic moments of the ions or from the spatial motion of the conduction electrons inside the material. Both description are given below.

Curie's law

For low levels of magnetization, the magnetization of paramagnets follows what is known as Curie's law, at least approximately. This law indicates that the susceptibility, , of paramagnetic materials is inversely proportional to their temperature, i.e. that materials become more magnetic at lower temperatures. The mathematical expression is:

where:

is the resulting magnetization, measured in amperes/meter (A/m),
is the volume magnetic susceptibility (dimensionless),
is the auxiliary magnetic field (A/m),
is absolute temperature, measured in kelvins (K),
is a material-specific Curie constant (K).

Curie's law is valid under the commonly encountered conditions of low magnetization (μBHkBT), but does not apply in the high-field/low-temperature regime where saturation of magnetization occurs (μBHkBT) and magnetic dipoles are all aligned with the applied field. When the dipoles are aligned, increasing the external field will not increase the total magnetization since there can be no further alignment.

For a paramagnetic ion with noninteracting magnetic moments with angular momentum J, the Curie constant is related the individual ions' magnetic moments,

where n is the number of atoms per unit volume. The parameter μeff is interpreted as the effective magnetic moment per paramagnetic ion. If one uses a classical treatment with molecular magnetic moments represented as discrete magnetic dipoles, μ, a Curie Law expression of the same form will emerge with μ appearing in place of μeff.

When orbital angular momentum contributions to the magnetic moment are small, as occurs for most organic radicals or for octahedral transition metal complexes with d3 or high-spin d5 configurations, the effective magnetic moment takes the form ( with g-factor ge = 2.0023... ≈ 2),

where Nu is the number of unpaired electrons. In other transition metal complexes this yields a useful, if somewhat cruder, estimate.

Pauli paramagnetism

For some alkali metals and noble metals, conductions electrons are weakly interacting and delocalized in space forming a Fermi gas. For these materials one contribution to the magnetic response comes from the interaction between the electron spins and the magnetic field known as Pauli paramagnetism. For a small magnetic field , the additional energy per electron from the interaction between an electron spin and the magnetic field is given by:

where is the vacuum permeability, is the electron magnetic moment, is the Bohr magneton, is the reduced Planck constant, and the g-factor cancels with the spin . The indicates that the sign is positive (negative) when the electron spin component in the direction of is parallel (antiparallel) to the magnetic field.

In a metal, the application of an external magnetic field increases the density of electrons with spins antiparallel with the field and lowers the density of the electrons with opposite spin. Note: The arrows in this picture indicate magnetic moment, not spin direction. Pauli 2bis.jpg
In a metal, the application of an external magnetic field increases the density of electrons with spins antiparallel with the field and lowers the density of the electrons with opposite spin. Note: The arrows in this picture indicate magnetic moment, not spin direction.

For low temperatures with respect to the Fermi temperature (around 104 kelvins for metals), the number density of electrons () pointing parallel (antiparallel) to the magnetic field can be written as:

with the total free-electrons density and the electronic density of states (number of states per energy per volume) at the Fermi energy .

In this approximation the magnetization is given as the magnetic moment of one electron times the difference in densities:

which yields a positive paramagnetic susceptibility independent of temperature:

The Pauli paramagnetic susceptibility is a macroscopic effect and has to be contrasted with Landau diamagnetic susceptibility which is equal to minus one third of Pauli's and also comes from delocalized electrons. The Pauli susceptibility comes from the spin interaction with the magnetic field while the Landau susceptibility comes from the spatial motion of the electrons and it is independent of the spin. In doped semiconductors the ratio between Landau's and Pauli's susceptibilities changes as the effective mass of the charge carriers can differ from the electron mass .

The magnetic response calculated for a gas of electrons is not the full picture as the magnetic susceptibility coming from the ions has to be included. Additionally, this formulas may break down for confined systems that differ from the bulk, like quantum dots, or for high fields, as demonstrated in the de Haas-van Alphen effect.

Pauli paramagnetism is named after the physicist Wolfgang Pauli. Before Pauli's theory, the lack of a strong Curie paramagnetism in metals was an open problem as the leading model could not account for this contribution without the use of quantum statistics.

Examples of paramagnets

Materials that are called "paramagnets" are most often those that exhibit, at least over an appreciable temperature range, magnetic susceptibilities that adhere to the Curie or Curie–Weiss laws. In principle any system that contains atoms, ions, or molecules with unpaired spins can be called a paramagnet, but the interactions between them need to be carefully considered.

Systems with minimal interactions

The narrowest definition would be: a system with unpaired spins that do not interact with each other. In this narrowest sense, the only pure paramagnet is a dilute gas of monatomic hydrogen atoms. Each atom has one non-interacting unpaired electron.

A gas of lithium atoms already possess two paired core electrons that produce a diamagnetic response of opposite sign. Strictly speaking Li is a mixed system therefore, although admittedly the diamagnetic component is weak and often neglected. In the case of heavier elements the diamagnetic contribution becomes more important and in the case of metallic gold it dominates the properties. The element hydrogen is virtually never called 'paramagnetic' because the monatomic gas is stable only at extremely high temperature; H atoms combine to form molecular H2 and in so doing, the magnetic moments are lost (quenched), because of the spins pair. Hydrogen is therefore diamagnetic and the same holds true for many other elements. Although the electronic configuration of the individual atoms (and ions) of most elements contain unpaired spins, they are not necessarily paramagnetic, because at ambient temperature quenching is very much the rule rather than the exception. The quenching tendency is weakest for f-electrons because f (especially 4f) orbitals are radially contracted and they overlap only weakly with orbitals on adjacent atoms. Consequently, the lanthanide elements with incompletely filled 4f-orbitals are paramagnetic or magnetically ordered. [4]

μeff values for typical d3 and d5 transition metal complexes. [5]
MaterialμeffB
[Cr(NH3)6]Br33.77
K3[Cr(CN)6]3.87
K3[MoCl6]3.79
K4[V(CN)6]3.78
[Mn(NH3)6]Cl25.92
(NH4)2[Mn(SO4)2]·6H2O5.92
NH4[Fe(SO4)2]·12H2O5.89

Thus, condensed phase paramagnets are only possible if the interactions of the spins that lead either to quenching or to ordering are kept at bay by structural isolation of the magnetic centers. There are two classes of materials for which this holds:

Systems with interactions

Idealized Curie-Weiss behavior; N.B. TC=th, but TN is not th. Paramagnetic regimes are denoted by solid lines. Close to TN or TC the behavior usually deviates from ideal. Para-ferro-anti.jpg
Idealized Curie–Weiss behavior; N.B. TC=θ, but TN is not θ. Paramagnetic regimes are denoted by solid lines. Close to TN or TC the behavior usually deviates from ideal.

As stated above, many materials that contain d- or f-elements do retain unquenched spins. Salts of such elements often show paramagnetic behavior but at low enough temperatures the magnetic moments may order. It is not uncommon to call such materials 'paramagnets', when referring to their paramagnetic behavior above their Curie or Néel-points, particularly if such temperatures are very low or have never been properly measured. Even for iron it is not uncommon to say that iron becomes a paramagnet above its relatively high Curie-point. In that case the Curie-point is seen as a phase transition between a ferromagnet and a 'paramagnet'. The word paramagnet now merely refers to the linear response of the system to an applied field, the temperature dependence of which requires an amended version of Curie's law, known as the Curie–Weiss law:

This amended law includes a term θ that describes the exchange interaction that is present albeit overcome by thermal motion. The sign of θ depends on whether ferro- or antiferromagnetic interactions dominate and it is seldom exactly zero, except in the dilute, isolated cases mentioned above.

Obviously, the paramagnetic Curie–Weiss description above TN or TC is a rather different interpretation of the word "paramagnet" as it does not imply the absence of interactions, but rather that the magnetic structure is random in the absence of an external field at these sufficiently high temperatures. Even if θ is close to zero this does not mean that there are no interactions, just that the aligning ferro- and the anti-aligning antiferromagnetic ones cancel. An additional complication is that the interactions are often different in different directions of the crystalline lattice (anisotropy), leading to complicated magnetic structures once ordered.

Randomness of the structure also applies to the many metals that show a net paramagnetic response over a broad temperature range. They do not follow a Curie type law as function of temperature however, often they are more or less temperature independent. This type of behavior is of an itinerant nature and better called Pauli-paramagnetism, but it is not unusual to see, for example, the metal aluminium called a "paramagnet", even though interactions are strong enough to give this element very good electrical conductivity.

Superparamagnets

Some materials show induced magnetic behavior that follows a Curie type law but with exceptionally large values for the Curie constants. These materials are known as superparamagnets. They are characterized by a strong ferromagnetic or ferrimagnetic type of coupling into domains of a limited size that behave independently from one another. The bulk properties of such a system resembles that of a paramagnet, but on a microscopic level they are ordered. The materials do show an ordering temperature above which the behavior reverts to ordinary paramagnetism (with interaction). Ferrofluids are a good example, but the phenomenon can also occur inside solids, e.g., when dilute paramagnetic centers are introduced in a strong itinerant medium of ferromagnetic coupling such as when Fe is substituted in TlCu2Se2 or the alloy AuFe. Such systems contain ferromagnetically coupled clusters that freeze out at lower temperatures. They are also called mictomagnets.

See also

Related Research Articles

Diamagnetism magnetic ordering

Diamagnetic materials are repelled by a magnetic field; an applied magnetic field creates an induced magnetic field in them in the opposite direction, causing a repulsive force. In contrast, paramagnetic and ferromagnetic materials are attracted by a magnetic field. Diamagnetism is a quantum mechanical effect that occurs in all materials; when it is the only contribution to the magnetism, the material is called diamagnetic. In paramagnetic and ferromagnetic substances the weak diamagnetic force is overcome by the attractive force of magnetic dipoles in the material. The magnetic permeability of diamagnetic materials is less than μ0, the permeability of vacuum. In most materials diamagnetism is a weak effect which can only be detected by sensitive laboratory instruments, but a superconductor acts as a strong diamagnet because it repels a magnetic field entirely from its interior.

Superparamagnetism is a form of magnetism which appears in small ferromagnetic or ferrimagnetic nanoparticles. In sufficiently small nanoparticles, magnetization can randomly flip direction under the influence of temperature. The typical time between two flips is called the Néel relaxation time. In the absence of an external magnetic field, when the time used to measure the magnetization of the nanoparticles is much longer than the Néel relaxation time, their magnetization appears to be in average zero; they are said to be in the superparamagnetic state. In this state, an external magnetic field is able to magnetize the nanoparticles, similarly to a paramagnet. However, their magnetic susceptibility is much larger than that of paramagnets.

Permeability (electromagnetism) measure of the ability of a material to support the formation of a magnetic field within itself

In electromagnetism, permeability is the measure of the ability of a material to support the formation of a magnetic field within itself, otherwise known as distributed inductance in transmission line theory. Hence, it is the degree of magnetization that a material obtains in response to an applied magnetic field. Magnetic permeability is typically represented by the (italicized) Greek letter μ. The term was coined in September 1885 by Oliver Heaviside. The reciprocal of magnetic permeability is magnetic reluctivity.

The Curie constant is a material-dependent property that relates a material's magnetic susceptibility to its temperature.

The Curie–Weiss law describes the magnetic susceptibility χ of a ferromagnet in the paramagnetic region above the Curie point:

Electron paramagnetic resonance technique to study materials with unpaired electrons

Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials with unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but it is electron spins that are excited instead of the spins of atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes or organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford.

Ferromagnetic resonance, or FMR, is a spectroscopic technique to probe the magnetization of ferromagnetic materials. It is a standard tool for probing spin waves and spin dynamics. FMR is very broadly similar to electron paramagnetic resonance (EPR), and also somewhat similar to nuclear magnetic resonance (NMR), except that FMR probes the sample magnetization resulting from the magnetic moments of dipolar-coupled but unpaired electrons, while NMR probes the magnetic moment of atomic nuclei that are screened by the atomic or molecular orbitals surrounding such nuclei of non-zero nuclear spin.

Magnetic structure ordered arrangement of magnetic spins in a material

The term magnetic structure of a material pertains to the ordered arrangement of magnetic spins, typically within an ordered crystallographic lattice. Its study is a branch of solid-state physics.

Electron nuclear double resonance (ENDOR) is a magnetic resonance technique for elucidating the molecular and electronic structure of paramagnetic species. The technique was first introduced to resolve interactions in electron paramagnetic resonance (EPR) spectra. It is currently practiced in a variety of modalities, mainly in the areas of biophysics and heterogeneous catalysis.

In a paramagnetic material, the magnetization of the material is (approximately) directly proportional to an applied magnetic field. However, if the material is heated, this proportionality is reduced: for a fixed value of the field, the magnetization is (approximately) inversely proportional to temperature. This fact is encapsulated by Curie's law, after Pierre Curie:

Magnetochemistry is concerned with the magnetic properties of chemical compounds. Magnetic properties arise from the spin and orbital angular momentum of the electrons contained in a compound. Compounds are diamagnetic when they contain no unpaired electrons. Molecular compounds that contain one or more unpaired electrons are paramagnetic. The magnitude of the paramagnetism is expressed as an effective magnetic moment, μeff. For first-row transition metals the magnitude of μeff is, to a first approximation, a simple function of the number of unpaired electrons, the spin-only formula. In general, spin-orbit coupling causes μeff to deviate from the spin-only formula. For the heavier transition metals, lanthanides and actinides, spin-orbit coupling cannot be ignored. Exchange interaction can occur in clusters and infinite lattices, resulting in ferromagnetism, antiferromagnetism or ferrimagnetism depending on the relative orientations of the individual spins.

References

  1. Miessler, G. L. and Tarr, D. A. (2010) Inorganic Chemistry 3rd ed., Pearson/Prentice Hall publisher, ISBN   0-13-035471-6.
  2. paramagnetism. Encyclopædia Britannica
  3. Nave, Carl L. "Magnetic Properties of Solids". HyperPhysics. Retrieved 2008-11-09.
  4. Jensen, J. & MacKintosh, A. R. (1991). Rare Earth Magnetism. Oxford: Clarendon Press.
  5. Orchard, A. F. (2003) Magnetochemistry. Oxford University Press.

Further reading