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 theDelocalization
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 as 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 likeMolecular 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 descriptions are given below.Curie's law
For low levels of magnetization, the magnetization of paramagnets follows what is known asPauli paramagnetism
For some alkali metals and noble metals, conduction 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. 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, these 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 Drude model could not account for this contribution without the use of quantum statistics. Pauli paramagnetism and Landau diamagnetism are essentially applications of the spin and the free electron model, the first is due to intrinsic spin of electrons; the second is due to their orbital motion.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 4''f'') 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. 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: *Molecular materials with a (isolated) paramagnetic center. ** Good examples are coordination complexes of d- or f-metals or proteins with such centers, e.g. myoglobin. In such materials the organic part of the molecule acts as an envelope shielding the spins from their neighbors. ** Small molecules can be stable in radical form, oxygen O2 is a good example. Such systems are quite rare because they tend to be rather reactive. * Dilute systems. ** Dissolving a paramagnetic species in a diamagnetic lattice at small concentrations, e.g. Nd3+ in CaCl2 will separate the neodymium ions at large enough distances that they do not interact. Such systems are of prime importance for what can be considered the most sensitive method to study paramagnetic systems: EPR.Systems with interactions
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 ''T''N or ''T''C is a rather different interpretation of the word "paramagnet" as it does ''not'' imply the ''absence'' of interactions, but rather that theSuperparamagnets
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
*References
Further reading
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