Editing Dynamic nuclear polarization (section)

==Mechanisms==

===Overhauser effect===
DNP was first realized using the concept of the Overhauser effect, which is the perturbation of nuclear [[Spin (physics)|spin]] level populations observed in metals and free radicals when electron spin transitions are saturated by microwave irradiation. This effect relies on stochastic interactions between an electron and a nucleus. The "dynamic" initially meant to highlight the time-dependent and random interactions in this polarization transfer process.

The DNP phenomenon was theoretically predicted by [[Albert Overhauser]] in 1953 <ref name="Overhauser">
{{cite journal
|last =Overhauser
|first = A.W.
|title = Polarization of Nuclei in Metals
|journal = [[Phys. Rev.]]
|volume = 92 |pages = 411–415
|year = 1953
|doi = 10.1103/PhysRev.92.411
|issue = 2 |bibcode = 1953PhRv...92..411O
}}</ref>
and initially drew some criticism from [[Norman Ramsey]], [[Felix Bloch]], and other renowned physicists of the time on the grounds of being "thermodynamically improbable". The experimental confirmation by Carver and [[Charles Pence Slichter|Slichter]]<ref name="Slichter">
{{cite journal
| last1       = Carver
| first1      = T.R.
| last2 = Slichter
| first2 = C.P.
| date       = 1953
| title      = Polarization of Nuclear Spins in Metals
| journal    = [[Phys. Rev.]]
| volume     = 92
| issue      = 1
| pages      = 212–213
| doi      = 10.1103/PhysRev.92.212.2
| bibcode = 1953PhRv...92..212C
}}</ref> as well as an apologetic letter from Ramsey both reached Overhauser in the same year.<ref name="ramsey">[http://www.physics.purdue.edu/about_us/history/Albert_W_Overhauser.shtml Purdue University Obituary of Albert W. Overhauser] {{webarchive|url=https://web.archive.org/web/20060109074625/http://www.physics.purdue.edu/about_us/history/Albert_W_Overhauser.shtml |date=2006-01-09 }}</ref>

The so-called electron-nucleus cross-relaxation, which is responsible for the DNP phenomenon is caused by rotational and translational modulation of the electron-nucleus [[hyperfine coupling]]. The theory of this process is based essentially on the second-order time-dependent [[perturbation theory]] solution of the [[von Neumann equation]] for the spin [[density matrix]].

While the Overhauser effect relies on time-dependent electron-nuclear interactions, the remaining polarizing mechanisms rely on time-independent electron-nuclear and electron-electron interactions.

===Solid effect===
The simplest spin system exhibiting the SE DNP mechanism is an electron-nucleus spin pair. The Hamiltonian of the system can be written as:

:<math>H_0=\omega_eS_z+\omega_{\rm n}I_z+AS_zI_z+B\ S_zI_x</math>

These terms are referring respectively to the electron and nucleus Zeeman interaction with the external magnetic field, and the hyperfine interaction. S and I are the electron and nuclear spin operators in the Zeeman basis (spin {{frac|1|2}} considered for simplicity), ''ω<sub>e</sub>'' and ''ω''<sub>n</sub> are the electron and nuclear [[Larmor precession|Larmor frequencies]], and ''A'' and ''B'' are the secular and pseudo-secular parts of the hyperfine interaction. For simplicity we will only consider the case of |''A''|,|''B''|<<|''ω''<sub>n</sub>|. In such a case ''A'' has little effect on the evolution of the spin system. During DNP a MW irradiation is applied at a frequency ''ω''<sub>MW</sub> and intensity ''ω''<sub>1</sub>, resulting in a rotating frame Hamiltonian given by
:<math>H=\Delta\omega_e\;S_z+\omega_{\rm n}I_z+AS_zI_z+B\ S_zI_x+\omega_1 S_x</math>where <math>\Delta\omega_e=\omega_e-\omega_{\rm MW}</math>

The MW irradiation can excite the electron single quantum transitions ("allowed transitions") when ''ω''<sub>MW</sub> is close to ''ω''<sub>e</sub>, resulting in a loss of the electron polarization. In addition, due to the small state mixing caused by the B term of the hyperfine interaction, it is possible to irradiate on the electron-nucleus zero quantum or double quantum ("forbidden") transitions around ''ω''<sub>MW</sub> = ''ω''<sub>e</sub> ± ''ω''<sub>n</sub>, resulting in polarization transfer between the electrons and the nuclei. The effective MW irradiation on these transitions is approximately given by ''Bω''<sub>1</sub>/2''ω''<sub>n</sub>.

====Static sample case====
In a simple picture of an electron-nucleus two-spin system, the solid effect occurs when a transition involving an electron-nucleus mutual flip (called zero quantum or double quantum) is excited by a microwave irradiation, in the presence of relaxation. This kind of transition is in general weakly allowed, meaning that the transition moment for the above microwave excitation results from a second-order effect of the electron-nuclear interactions and thus requires stronger microwave power to be significant, and its intensity is decreased by an increase of the external magnetic field B<sub>0</sub>. As a result, the DNP enhancement from the solid effect scales as B<sub>0</sub><sup>−2</sup> when all the relaxation parameters are kept constant. Once this transition is excited and the relaxation is acting, the magnetization is spread over the "bulk" nuclei (the major part of the detected nuclei in an NMR experiment) via the nuclear dipole network.
This polarizing mechanism is optimal when the exciting microwave frequency shifts up or down by the nuclear Larmor frequency from the electron Larmor frequency in the discussed two-spin system. The direction of frequency shifts corresponds to the sign of DNP enhancements.
Solid effect exist in most cases but is more easily observed if the linewidth of the EPR spectrum of involved [[unpaired electron]]s is smaller than the nuclear Larmor frequency of the corresponding nuclei.

====Magic angle spinning case====
In the case of magic angle spinning DNP (MAS-DNP), the mechanism is different but to understand it, a two spins system can still be used. The polarization process of the nucleus still occurs when the microwave irradiation excites the double quantum or zero quantum transition, but due to the fact that the sample is spinning, this condition is only met for a short time at each rotor cycle (which makes it periodical). The DNP process in that case happens step by step and not continuously as in the static case.<ref name="Mentink-Vigier, F. Akbey, U. Hovav, Y. Vega, S. Oschkinat, H. Feintuch, A. 2012 13–21">{{cite journal
|author = Mentink-Vigier, F.
|author2 = Akbey, U.
|author3 = Hovav, Y.
|author4 = Vega, S.
|author5 = Oschkinat, H.
|author6 = Feintuch, A.
|title = Fast passage dynamic nuclear polarization on rotating solids
|journal = [[J. Mag. Reson.]]
|volume = 224 |pages = 13–21
|year = 2012
|doi = 10.1016/j.jmr.2012.08.013
|pmid = 23000976
|bibcode = 2012JMagR.224...13M
}}</ref>

===Cross effect===

====Static case====
The cross effect requires two unpaired electrons as the source of high polarization. Without special condition, such a three spins system can only generate a solid effect type of polarization. However, when the resonance frequency of each electron is separated by the nuclear Larmor frequency, and when the two electrons are dipolar coupled, another mechanism occurs: the cross-effect. In that case, the DNP process is the result of irradiation of an allowed transition (called single quantum) as a result the strength of microwave irradiation is less demanded than that in the solid effect. In practice, the correct EPR frequency separation is accomplished through random orientation of paramagnetic species with g-anisotropy. Since the "frequency" distance between the two electrons should be equal to the Larmor frequency of the targeted nucleus, cross-effect can only occur if the inhomogeneously broadened EPR lineshape has a linewidth broader than the nuclear Larmor frequency. Therefore, as this linewidth is proportional to external magnetic field B<sub>0</sub>, the overall DNP efficiency (or the enhancement of nuclear polarization) scales as B<sub>0</sub><sup>−1</sup>. This remains true as long as the relaxation times remain constant. Usually going to higher field leads to longer nuclear relaxation times and this may partially compensate for the line broadening reduction.
In practice, in a glassy sample, the probability of having two dipolarly coupled electrons separated by the Larmor frequency is very scarce. Nonetheless, this mechanism is so efficient that it can be experimentally observed alone or in addition to the solid-effect.<ref name=":0" /><ref>{{Cite journal |last=Abragam |first=A |last2=Goldman |first2=M |date=1978-03-01 |title=Principles of dynamic nuclear polarisation |url=http://dx.doi.org/10.1088/0034-4885/41/3/002 |journal=Reports on Progress in Physics |volume=41 |issue=3 |pages=395–467 |doi=10.1088/0034-4885/41/3/002 |issn=0034-4885|url-access=subscription }}</ref>

====Magic angle spinning case====
As in the static case, the MAS-DNP mechanism of cross effect is deeply modified due to the time dependent [[energy level]]. By taking a simple three spin system, it has been demonstrated that the cross-effect mechanism is different in the Static and MAS case. The cross effect is the result of very fast multi-step process involving EPR single quantum transition, electron dipolar anti-crossing and cross effect degeneracy conditions.
In the most simple case the MAS-DNP mechanism can be explained by the combination of a single quantum transition followed by the cross-effect degeneracy condition, or by the electron-dipolar anti-crossing followed by the cross-effect degeneracy condition.<ref name="Mentink-Vigier, F. Akbey, U. Hovav, Y. Vega, S. Oschkinat, H. Feintuch, A. 2012 13–21"/><ref name=tycko12>
{{cite journal
|author =Thurber, K. R. |author2=Tycko, R.
|title = Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: the importance of level crossings
|journal = [[J. Chem. Phys.]]
|volume = 137 |pages = 084508
|year = 2012
|doi = 10.1063/1.4747449
|pmid=22938251
|issue = 8 |bibcode = 2012JChPh.137h4508T
|pmc = 3443114}}</ref>

This in turn change dramatically the CE dependence over the static magnetic field which does not scale like B<sub>0</sub><sup>−1</sup> and makes it much more efficient than the solid effect.<ref name=tycko12 />

===Thermal mixing===
Thermal mixing is an energy exchange phenomenon between the electron spin ensemble and the nuclear spin, which can be thought of as using multiple electron spins to provide hyper-nuclear polarization. Note that the electron spin ensemble acts as a whole because of stronger inter-electron interactions. The strong interactions lead to a homogeneously broadened EPR lineshape of the involved paramagnetic species. The linewidth is optimized for polarization transfer from electrons to nuclei, when it is close to the nuclear Larmor frequency. The optimization is related to an embedded three-spin (electron-electron-nucleus) process that mutually flips the coupled three spins under the energy conservation (mainly) of the Zeeman interactions. Due to the inhomogeneous component of the associated EPR lineshape, the DNP enhancement by this mechanism also scales as B<sub>0</sub><sup>−1</sup>.

===DNP-NMR enhancement curves===

[[File:Dnp350-01.png|thumb|right|400px|<sup>1</sup>H DNP-NMR enhancement curve for cellulose char heated for several hours at 350 °C. P<sub>H</sub> − 1 is the relative polarization or intensity of the <sup>1</sup>H signal.]]

Many types of solid materials can exhibit more than one mechanism for DNP. Some examples are carbonaceous materials such bituminous coal and charcoal (wood or cellulose heated at high temperatures above their decomposition point which leaves a residual solid char). To separate out the mechanisms of DNP and to characterize the electron-nuclear interactions occurring in such solids a DNP enhancement curve can be made. A typical enhancement curve is obtained by measuring the maximum intensity of the NMR [[free induction decay|FID]] of the <sup>1</sup>H nuclei, for example, in the presence of continuous microwave irradiation as a function of the microwave frequency offset.

Carbonaceous materials such as cellulose char contain large numbers of stable free electrons delocalized in large [[polycyclic aromatic hydrocarbon]]s. Such electrons can give large polarization enhancements to nearby protons via proton-proton spin-diffusion if they are not so close together that the electron-nuclear dipolar interaction does not broaden the proton resonance beyond detection. For small isolated clusters, the free electrons are fixed and give rise to solid-state enhancements (SS). The maximal proton solid-state enhancement is observed at microwave offsets of ω ≈ ω<sub>e</sub> ± ω<sub>H</sub>, where ω<sub>e</sub> and ω<sub>H</sub> are the electron and nuclear Larmor frequencies, respectively. For larger and more densely concentrated aromatic clusters, the free electrons can undergo rapid [[exchange interaction|electron exchange interactions]]. These electrons give rise to an Overhauser enhancement centered at a microwave offset of ω<sub>e</sub> − ω<sub>H</sub> = 0. The cellulose char also exhibits electrons undergoing thermal mixing effects (TM). While the enhancement curve reveals the types electron-nuclear spin interactions in a material, it is not quantitative and the relative abundance of the different types of nuclei cannot be determined directly from the curve.<ref>{{Cite journal
|last1=Wind
|first1=R.A.
|last2=Li
|first2=L.
|last3=Maciel
|first3=G.E.
|last4=Wooten
|first4=J.B.
|title=Characterization of Electron Spin Exchange Interactions in Cellulose Chars by Means of ESR, 1H NMR, and Dynamic Nuclear Polarization
|journal=Applied Magnetic Resonance
|year=1993
|volume=5
|issue=2
|pages=161–176
|issn=0937-9347
|doi=10.1007/BF03162519|s2cid=96672106
}}
</ref>
{{clear}}

===DNP-NMR===
DNP can be performed to enhance NMR signals but also to introduce an inherent spatial dependence: the magnetization enhancement takes place in the vicinity of the irradiated electrons and propagates throughout the sample. Spatial selectivity can finally be obtained using [[magnetic resonance imaging]] (MRI) techniques, so that signals from similar parts can be separated based on their location in the sample.<ref>{{cite journal |last1=Moroz |first1=Ilia B. |last2=Leskes |first2=Michal |title=Dynamic Nuclear Polarization Solid-State NMR Spectroscopy for Materials Research |journal=Annual Review of Materials Research |date=1 July 2022 |volume=52 |issue=1 |pages=25–55 |doi=10.1146/annurev-matsci-081720-085634 |bibcode=2022AnRMS..52...25M |s2cid=247375660 |url=https://www.annualreviews.org/doi/abs/10.1146/annurev-matsci-081720-085634 |language=en |issn=1531-7331|doi-access=free }}</ref><ref name="sciencedirect.com">{{cite journal |last1=Bagheri |first1=Khashayar |last2=Deschamps |first2=Michael |last3=Salager |first3=Elodie |title=Nuclear magnetic resonance for interfaces in rechargeable batteries |journal=Current Opinion in Colloid & Interface Science |date=1 April 2023 |volume=64 |pages=101675 |doi=10.1016/j.cocis.2022.101675 |s2cid=255364390 |url=https://hal.science/hal-03925315/file/20221126_COCIS_revised.pdf |language=en |issn=1359-0294}}</ref>
DNP has triggered enthusiasm in the NMR community because it can enhance sensitivity in [[Solid-state nuclear magnetic resonance|solid-state NMR]]. In DNP, a large electronic [[spin polarization]] is transferred onto the nuclear spins of interest using a microwave source. There are two main DNP approaches for solids. If the material does not contain suitable unpaired electrons, exogenous DNP is applied: the material is impregnated by a solution containing a specific radical. When possible, endogenous DNP is performed using the electrons in [[transition metal]] ions (metal-ion dynamic nuclear polarization, MIDNP) or [[Valence and conduction bands|conduction electrons]]. The experiments usually need to be performed at low temperatures with [[magic angle spinning]]. It is important to note that DNP was only performed ex situ as it usually requires low temperature to lower electronic relaxation.<ref name="sciencedirect.com"/>