Spinning-Driven Dynamic Nuclear Polarization with Optical Pumping.

The massive development of portable electronics, electric vehicles, and the increased need for energy storage require higher battery energy density, improved efficiency, and safety. In this context, lithium metal is the ultimate high-energy-density battery anode material. However, its use as an anode material is limited due to the formation of lithium dendrites that could lead to low efficiency and potential safety issues. Therefore, understanding and controlling the formation of lithium dendrites is key to realise lithium metal batteries.Here we show a new approach combining Scanning Electron Microscopy (SEM) and Magic-Angle Spinning Dynamic Nuclear Polarization (MAS DNP) to study the interplay between lithium morphology and interface reactivity. We aim to understand how the Solid-Electrolyte-Interphase (SEI), formed at the surface of lithium metal, affects lithium morphology. 1,2. Whereas the morphology of lithium dendrites can easily be identified using SEM, information about the SEI is more challenging to access. Among the different techniques used to characterize battery material, Nuclear Magnetic Resonance (NMR), has emerged as a powerful method providing information about the chemical composition as well as dynamic properties of a given material, at the atomic scale. Yet, the main limitations of NMR are its low intrinsic sensitivity and lack of selectivity which highly complicate the study of thin interphase as the SEI. In the present work, we use MAS DNP to overcome the low sensitivity of NMR. MAS DNP is based on the transfer of the large electron spin polarization of unpaired electrons to the nuclear spins, leading to the enhancement of the NMR signal intensity. However, the addition of free organic radicals solution to the typical exogenous DNP may alter the nature of the SEI. Furthermore, exogenous DNP is not selective to the interfaces between the lithium metal and the SEI. In this respect, we use the recently developed Lithium metal DNP method which exploits lithium metal's conduction electrons to perform endogenous MAS DNP and achieve one order of magnitude hyperpolarization at room temperature3. In addition to the gain of sensitivity, this technique allows to selectively enhance the chemical species close to the lithium metal providing critical information about the chemical structure of the SEI. This approach, currently under development, provides a powerful tool in research to control and prevent the formation of lithium dendrites which typically result in rapid degradation and potential safety issues. Figure: A) Schematic representation of Lithium dendrites with SEM of lithium dendrites formed on a copper current collector. B) Schematic representation of SEI formed on lithium metal with 7Li MAS DNP spectra recorded with and without microwave irradiation on lithium dendrites

Perspectives on microwave coupling into cylindrical and spherical rotors with dielectric lenses for magic angle spinning dynamic nuclear polarization.

Impact of non-polar solvents in dynamic nuclear polarization at high magnetic fields.

Understanding the spatial distribution of the P1 centers is crucial for diamond-based sensors and quantum devices. P1 centers serve as polarization sources for dynamic nuclear polarization (DNP) quantum sensing and play a significant role in the relaxation of nitrogen vacancy (NV) centers. Additionally, the distribution of NV centers correlates with the distribution of P1 centers, as NV centers are formed through the conversion of P1 centers. We utilized DNP and pulsed electron paramagnetic resonance (EPR) techniques that revealed strong clustering of a significant population of P1 centers that exhibit exchange coupling and produce asymmetric line shapes. The 13C DNP frequency profile at a high magnetic field revealed a pattern that requires an asymmetric EPR line shape of the P1 clusters with electron-electron (e-e) coupling strengths exceeding the 13C nuclear Larmor frequency. EPR and DNP characterization at high magnetic fields was necessary to resolve energy contributions from different e-e couplings. We employed a two-frequency pump-probe pulsed electron double resonance technique to show cross-talk between the isolated and clustered P1 centers. This finding implies that the clustered P1 centers affect all of the P1 populations. Direct observation of clustered P1 centers and their asymmetric line shape offers a novel and crucial insight into understanding magnetic noise sources for quantum information applications of diamonds and for designing diamond-based polarizing agents with optimized DNP efficiency for 13C and other nuclear spins of analytes. We propose that room temperature 13C DNP at a high field, achievable through straightforward modifications to existing solution-state NMR systems, is a potent tool for evaluating and controlling diamond defects.

Dynamic nuclear polarization (DNP) at low temperature (1.2 K) and high magnetic field (3.3 T) was applied to a contrast variation study in small-angle neutron scattering (SANS) focusing on industrial rubber materials. By varying the scattering contrast by DNP, time-of-flight SANS profiles were obtained at the pulsed neutron source of the Japan Proton Accelerator Research Complex (J-PARC). The concentration of a small organic molecule, (2,2,6,6-tetramethylpiperidine-1-yl)oxy (TEMPO), was carefully controlled by a doping method using vapour sorption into the rubber specimens. With the assistance of microwave irradiation (94 GHz), almost full polarization of the paramagnetic electronic spin of TEMPO was transferred to the spin state of hydrogen (protons) in the rubber materials to obtain a high proton spin polarization (PH). The following samples were prepared: (i) a binary mixture of styrene-butadiene random copolymer (SBR) with silica particles (SBR/SP); and (ii) a ternary mixture of SBR with silica and carbon black particles (SBR/SP/CP). For the binary mixture (SBR/SP), the intensity of SANS significantly increased or decreased while keeping its q dependence for PH = -35% or PH = 40%, respectively. The q behaviour of SANS for the SBR/SP mixture can be reproduced using the form factor of a spherical particle. The intensity at low q (∼0.01 Å-1) varied as a quadratic function of PH and indicated a minimum value at PH = 30%, which can be explained by the scattering contrast between SP and SBR. The scattering intensity at high q (∼0.3 Å-1) decreased with increasing PH, which is attributed to the incoherent scattering from hydrogen. For the ternary mixture (SBR/SP/CP), the q behaviour of SANS was varied by changing PH. At PH = -35%, the scattering maxima originating from the form factor of SP prevailed, whereas at PH = 29% and PH = 38%, the scattering maxima disappeared. After decomposition of the total SANS according to inverse matrix calculations, the partial scattering functions were obtained. The partial scattering function obtained for SP was well reproduced by a spherical form factor and matched the SANS profile for the SBR/SP mixture. The partial scattering function for CP exhibited surface fractal behaviour according to q-3.6, which is consistent with the results for the SBR/CP mixture.

Breaking the maximum enhancement barrier of 660 at room temperature in a conventional dynamic nuclear polarization (DNP) experiment has the immense potential of practical applications. Optical DNP experiments with radical-chromophore (RC) adducts, which harnesses hyperpolarized radicals, instead of thermalized radicals, offers a powerful way to achieve this. Typical DNP and NMR experiments, however, are carried out at high magnetic fields of about 5-10 T, whereas the large electron spin hyperpolarization (ESP) demonstrated in the RC adducts so far are at a much low field of 0.3 T. Thus, in order to realize a successful optical DNP experiment, it is imperative to ask whether the RC adducts, which are currently available, can achieve a large ESP even at high fields. The present work poses this question and shows that the current RC adducts would not generate a large ESP at high fields unless the separation between the chromophore and nitroxyl moiety is reduced to less than four bonds. Two serious bottlenecks in this direction are the near impossibility of synthesizing such RC adducts using the common nitroxyl radicals and the absence of any photophysical studies on RC adducts with such short spacer groups. In this regard, the present work exploits the spin trapping methodology to synthesize one- and two-atom separated naphthalene-nitroxyl RC adducts. Good yields and excellent stability of the adducts have been demonstrated. Furthermore, the present work presents their detailed photophysical and photochemical studies by transient optical and time-resolved EPR studies. On the basis of the present results, a potential RC adduct is proposed for the high field optical DNP experiments. Finally, the prospect of exploiting the large EPR signal enhancement due to ESP in the field of spin trapping studies has been discussed.

Solid-state MAS NMR at ultra low temperature of hydrated alanine doped with DNP radicals

The goal of dynamic nuclear polarization (DNP) is to enhance NMR signals by transferring electron spin polarization to the nuclei. Although mechanisms such as the solid effect and thermal mixing can be used for DNP in the solid state, currently, the only practical mechanism in solutions is the Overhauser effect (OE), which usually arises due to dipolar relaxation between electrons and the nuclei. At magnetic fields greater than approximately 1 T, dipolar relaxation does not result in a useful enhancement and therefore the conventional wisdom is that DNP should not work in solutions at high magnetic fields. However, scalar relaxation due to time-dependent scalar couplings has a different magnetic field dependence and can lead to substantial OE enhancements. At room temperature and at a magnetic field of 5 T (211 MHz for protons, 140 GHz for electrons), we have observed that scalar relaxation between electrons and nuclei results in NMR signal enhancements of 180, 42, -36, and 8, for 31P, 13C, 15N, and 19F, respectively.

Magnetic anisotropy of some phyllosilicates

Pairing the spectral resolution provided by high magnetic fields at ambient temperature with the enhanced sensitivity offered by dynamic nuclear polarization (DNP) is a major goal of modern solid-state NMR spectroscopy, which will allow one to unlock ever-challenging applications. This study demonstrates that, by combining HyTEK2, a hybrid BDPA-nitroxide biradical polarizing agent, with ortho-terphenyl (OTP), a rigid DNP matrix, enhancement factors as high as 65 can be obtained at 230 K, 40 kHz magic angle spinning (MAS), and 18.8 T. The temperature dependence of the DNP enhancement and its behavior around the glass transition temperature (Tg) of the matrix is investigated by variable-temperature EPR measurements of the electron relaxation properties and numerical simulations. A correlation is suggested between the decrease in enhancement at the passage of the Tg and the concomitant drop of both transverse electron relaxation times in the biradical.

High magnetic field is an important research condition which can provide great opportunities for the development of many subjects. Since 1913, there are 19 Nobel Prizes which are related to high magnetic field. Scientific research under high magnetic field involves a large amount of subjects and various scientific issues. In many research areas such as the quantum transport in semiconductors, Fermi surface measurements, the study of the upper critical field of high temperature superconductors, nuclear magnetic resonance study etc., high magnetic field is an essential condition. Therefore, the scientific research under high magnetic field is always the frontier. In this review, the cutting-edge scientific issues under high magnetic field are presented. The issues in physics include the fractional quantum Hall effect in graphene, the quantum oscillations in black phosphorus, the topological insulator Bi2Se3, the Weyl semimetal NbP, the quantum ordering in non-conventional superconductor, the magnetic field induced new superconducting phase, the magnetic field induced metamagnetism transition, the quantum effect of low dimensional materials, the spin frustration, etc. In chemistry and material science, the focuses are magnetic field induced new chemical reaction, control of reaction routes, the reaction kinetics, synthesis of single molecular magnet and chiral materials, nano-catalysis, etc. Issues related to nuclear magnetic resonance are also mentioned, including the protein structure determination, magnetic resonance imaging for medical science, the structure of melt, geosciences and environmental sciences, etc. Moreover, the present condition and achievement of the high magnetic field facility in China are shown in the following part. Three water-cooled magnets have created three world records. The water-cooled magnet WM1 with a 32 mm bore can generate a steady magnetic field of 38.5 Tesla, which has exceeded the previous record 37.5 Tesla. The water-cooled magnet WM5 with a 50 mm bore has produced a magnetic field of 35 Tesla, which is also the highest for the same type of magnets. The water-cooled magnet WM4 with a 32 mm bore has generated a magnetic field of 27.5 Tesla when inputting 10 MW power. All the magnets have corresponding experimental systems. For example, WM1 has a 3He extreme low temperature experiment dewar installed providing a temperature region from 325 mK to 70 K, which is mainly used for transport measurement. The high-homogeneity water-cooled magnet WM2 has a high field high frequency (82 to 690 GHz) electron magnetic resonance continuous wave system installed. WM5 can cooperate with a Fourier transform infrared spectroscopy (18000 to 4000 cm - 1), a vibrating sample magnetometer for magnetization measurement, and a high pressure experiment system (0–200 GPa). The service of the high magnetic field facilities in China will provide strong support for various cutting-edge research and create advantage for significant original achievement.

In spite of its name, the solid effect of dynamic nuclear polarization (DNP) is also operative in viscous liquids, where the dipolar interaction between the polarized nuclear spins and the polarizing electrons is not completely averaged out by molecular diffusion on the timescale of the electronic spin-spin relaxation time. Under such slow-motional conditions, it is likely that the tumbling of the polarizing agent is similarly too slow to efficiently average the anisotropies of its magnetic tensors on the timescale of the electronic . Here we extend our previous analysis of the solid effect in liquids to account for the effect of -tensor anisotropy at high magnetic fields. Building directly on the mathematical treatment of slow tumbling in electron spin resonance , we calculate solid-effect DNP enhancements in the presence of both translational diffusion of the liquid molecules and rotational diffusion of the polarizing agent. To illustrate the formalism, we analyze high-field (9.4 T) DNP enhancement profiles from nitroxide-labeled lipids in fluid lipid bilayers. By properly accounting for power broadening and motional broadening, we successfully decompose the measured DNP enhancements into their separate contributions from the solid and Overhauser effects.

We report on the design and implementation of a spectral ellipsometer at near-infrared wavelength (700-1000 nm) for samples placed in high magnetic fields (up to 14 T) at low temperatures (~4.2 K). The main optical components are integrated in a probe, which can be inserted into a conventional long-neck He dewar and has a very long free-space optical path (~1.8 m×2). A polarizer-sample-(quarter-wave plate)-rotating analyzer configuration was employed. Two dielectric mirrors, one before and one after the sample in the optical path, helped to reflect the light back to the analyzer and a two-axis piezo-driven goniometer under the sample holder was used to control the direction of the reflected light. Functional test results performed on an intrinsic GaAs wafer and analysis on the random error of the system are shown. We obtained both amplitude and phase ellipsometric spectra simultaneously and observed helicity transformation at energies near the GaAs exciton transitions in the phase spectra. Significant shifts of them induced by magnetic fields were observed and fitted with a simple model. This system will allow us to study the collective magneto-optical response of materials and spatial dispersive exciton-polariton related problems in high external magnetic fields at low temperatures.

High magnetic fields have been of interest for some time in solid-state physics. Recent spectroscopic experiments on highly excited barium atoms and the discovery of very large magnetic fields in white dwarf stars and neutron stars have stimulated renewed interest in the spectroscopy of free atoms in high magnetic fields. The various spectroscopic regimes ranging from the low-field Zeeman effect to the high-field Landau regime are reviewed. Calculations of the energy levels of hydrogen, helium and their isoelectronic ions in fields of any strength are surveyed. Observations of the quadratic Zeeman effect in the alkalis and high-field effects in the neutral barium spectrum are described. Finally, recent discoveries of continuum polarization in white dwarf stars, its interpretation in terms of the presence of high magnetic fields, the confirmation of such fields spectroscopically, and some remaining mysteries in these remarkable stellar spectra are reviewed.

Organic light-emitting diodes with structure of ITO/CuPc/NPB/Alq 3 /BCP(x)/Al were fabricated in this work. The thickness of BCP is 40, 80 and 120 nm, respectively. The magnetic field effects on the conductance (magneto-conductance, MC) of these diodes were measured at temperature range from 300 to 15 K, respectively. Results show that the MC responses of all the three devices reveal a positive component under low magnetic field at all working temperatures. However, the MC effects under high magnetic field of the BCP(x)-inserted devices show a strong dependence on the temperature and device thickness. In particular, the MC of BCP (120nm) device shows a sign inversion as decreasing the temperature. However, this phenomenon can not be observed in the BCP (40, 80nm) devices. Only negative component of MC is existed in the two devices at low temperatures. We suggest that the positive MC in low magnetic field is caused by hyperfine interaction. Moreover, the sign inversion of MC at high magnetic field is caused by the interaction between the triplet excition with long lifetime at low temperature and holes which are intercalated by the BCP inserted layer.