Quadrupolar Spin Research Articles

可変型超伝導磁石による固体NMR 測定の新展開

可変型超伝導磁石による固体NMR 測定の新展開

Emergent SU(3) Symmetry in Random Spin-1 Chains.

We show that generic SU(2)-invariant random spin-1 chains have phases with an emergent SU(3) symmetry. We map out the full zero-temperature phase diagram and identify two different phases: (i)a conventional random-singlet phase (RSP) of strongly bound spin pairs [SU(3) "mesons"] and (ii)an unconventional RSP of bound SU(3) "baryons," which are formed, in the great majority, by spin trios located at random positions. The emergent SU(3) symmetry dictates that susceptibilities and correlation functions of both dipolar and quadrupolar spin operators have the same asymptotic behavior.

Introducing new half-integer quadrupolar nuclei for solid state NMR of inclusion compounds

Broad developments in experimental NMR techniques have opened new and exciting opportunities for application of solid state nuclear magnetic resonance (SS NMR) in studies of gas hydrates and inclusion compounds in general. Perhaps the most important advance of the last 10 years was the extension into very high magnetic fields beyond 20 T. This progress is especially significant in studies concerned with low-γ, low natural abundance, and quadrupolar nuclei. This work reports our recent exploration of clathrate hydrates and other inclusion compounds (β-quinol, tert-Bu-Calix[4], and dodecasil-3C) with SS NMR of nuclei that were not so long ago completely out of reach for NMR, namely 131Xe, 83Kr, and 33S. Although 129Xe is a widely used NMR probe, applications of the low-γ isotope 131Xe were very scarce. Being a quadrupolar spin 3/2 nucleus, 131Xe provides an additional probe for sampling the electric field gradients in inclusion compounds. Another nucleus that has been seriously under-explored is 83Kr, with its very low γ being the main obstacle, and along with quadrupolar coupling we report the first detection of the chemical shift anisotropy in krypton. The relative values of the Sternheimer antishielding factors for 131Xe and 83Kr, obtained by comparison of the spectra of the two in identical cage environments, are also discussed. Though 33S NMR of solids is notoriously difficult due to its low γ, low natural abundance, and relatively large quadrupolar moment, working at the field of 21.1 T it was possible to acquire, in a reasonable time, natural abundance 33S SS NMR spectra of various H2S and SO2 gas hydrates and inclusion compounds. In most cases the spectra are dominated by the quadrupolar interactions, providing information on the symmetry of the cages encapsulating the guest molecules, and also show the effects of very rapid reorientation of the encaged H2S and SO2. The impact of the introduction of new NMR nuclei on hydrate research is discussed.

An optimal double-magic flip angle for performing the distance measurement REDOR experiment on a spin S=1

Distance measurements between a half-spin and a quadrupolar S=1 spin having a small quadrupolar coupling constant can be performed using the rotational echo double resonance (REDOR) experiment. We derived an analytical expression for the probability of transitions between energy levels resulting from the application of an arbitrary pulse flip angle to the quadrupolar spin and consequently minimized the probability that populations of individual levels do not undergo a spin transition during the pulse. As a result we discovered that if the flip angle of the quadrupolar spin pulse is 109.47°, the maximal recoupling values are the largest possible and the signal reaches a maximum value of 8/9, larger than in the use of either a 90° pulse or a 180° pulse. In addition, the slope of the initial decay is higher than that of the 90° pulse. The recoupling signal can be modeled by an exact analytical formula in the ideal case and simulations show that the advantage of the 109.47° pulse is preserved when the quadrupolar coupling constant CQ has a finite value typical of 2H and 6Li spins (up to CQ~200kHz). Experimental results on two spin pairs, 2H–13C and 6Li–13C, demonstrate the validity and accuracy of this method.

25 Mg NMR Studies of Mg-Ion Battery Materials

Multivalent-ion chemistries such as Mg-ion are emerging as alternative battery systems to Li-ion. Current Mg-ion chemistries are limited to relatively low voltages and relatively low reversible specific capacities (1-2). Recent research on potential high voltage Mg-ion cathode materials and alternative anode materials such as transition metal oxides and metal alloys have highlighted the urgent need to understand structure activity relationships and insertion/intercalation phenomenon for development of such systems (3). Solid state NMR is a powerful tool to investigate local structure and insertion/intercalation phenomena, particularly for batteries as shown for Li-ion chemistries with 6Li and 7Li NMR (4, 5). However, the low natural abundance (10%) of the NMR active Mg isotope (25Mg), highly quadrupolar nuclear spin of 25Mg (spin 5/2) and very low gyromagnetic ratio (i.e 30.6 MHz Larmor frequency relative to 1H = 500 MHz) limits the effective use of 25Mg NMR for solid Mg-ion battery materials (6). In this work, despite the challenges of 25Mg NMR, our recent efforts to characterize Mg environments in cathode materials such as MgMn2O4 spinels, MgV2O5, in anode materials such as h-TiO2 and Mg alloys will be presented. Chemical magnesiation using dibutylmagnesium and preliminary electrochemical (de)magnesiation and the structural changes induced will be discussed. The results will summarize the effectiveness of the method in distinguishing side reactions or undesirable conversion reactions, including amorphous phases, from intercalation phenomenon. 1. D. Aurbach, Z. Lu, A. Schechter, Y. Gofer, H. Gizbar, R. Turgeman, Y. Cohen, M. Moshkovich, and E. Levi, Nature, 407 (6805), 724-727 (2000). 2. H. D. Yoo, I. Shterenberg, Y. Gofer, G. Gershinsky, N. Pour, and D. Aurbach, Energ Environ Sci, 6 (8), 2265-2279 (2013). 3. Magnesium Batteries 1 and 2, 224th Electrochemical Society Meeting, San Francisco CA, 2013 4. C. P. Grey and N. Dupre, Chem. Rev. (Washington, DC, U. S.), 104, 4493 (2004). 5. B. Key, R. Bhattacharyya, M. Morcrette, V. Seznec, J. M. Tarascon and C. P. Grey, Journal of the American Chemical Society, 131, 9239 (2009). 6. R. Dupree and M. E. Smith, Journal of the Chemical Society-Chemical Communications, 1483 (1988).

Spin-Spin Coupling between Quadrupolar Nuclei in Solids: (11)B-(75)As Spin Pairs in Lewis Acid-Base Adducts.

Solid-state (11)B NMR measurements of Lewis acid-base adducts of the form R3AsBR'3 (R = Me, Et, Ph; R' = H, Ph, C6F5) were carried out at several magnetic field strengths (e.g., B0 = 21.14, 11.75, and 7.05 T). The (11)B NMR spectra of these adducts exhibit residual dipolar coupling under MAS conditions, allowing for the determination of effective dipolar coupling constants, Reff((75)As,(11)B), as well as the sign of the (75)As nuclear quadrupolar coupling constants. Values of Reff((75)As,(11)B) range from 500 to 700 Hz. Small isotropic J-couplings are resolved in some cases, and the sign of (1)J((75)As,(11)B) is determined. Values of CQ((75)As) measured at B0 = 21.14 T for these triarylborane Lewis acid-base adducts range from -82 ± 2 MHz for Et3AsB(C6F5)3 to -146 ± 1 MHz for Ph3AsBPh3. For Ph3AsBH3, two crystallographically nonequivalent sites are identified with CQ((75)As) values of -153 and -151 ± 1 MHz. For the uncoordinated Lewis base, Ph3As, four (75)As sites with CQ((75)As) values ranging from 193.5 to 194.4 ± 2 MHz are identified. At these applied magnetic field strengths, the (75)As quadrupolar interaction does not satisfy high-field approximation criteria, and thus, an exact treatment was used to describe this interaction in (11)B and (75)As NMR spectral simulations. NMR parameters calculated using the ADF and CASTEP program packages support the experimentally derived parameters in both magnitude and sign. These experiments add to the limited body of literature on solid-state (75)As NMR spectroscopy and serve as examples of spin-spin-coupled quadrupolar spin pairs, which are also rarely treated in the literature.

I-Love-Q anisotropically: Universal relations for compact stars with scalar pressure anisotropy

Certain physical quantities that characterize neutron stars and quark stars (e.g. their mass, spin angular momentum and quadrupole moment) are interrelated in a way that is approximately insensitive to their internal structure. Such approximately universal relations are useful to break degeneracies in data analysis for future radio, X-ray and gravitational wave observations. Although the pressure inside compact stars is most likely nearly isotropic, certain scenarios have been put forth that suggest otherwise, for example due to phase transitions. We here investigate whether pressure anisotropy affects the approximate universal relations and whether it prevents their use in future observations. We achieve this by numerically constructing slowly-rotating and tidally-deformed, anisotropic, compact stars in General Relativity to third order in spin. We find that anisotropy affects the universal relations only weakly; the relations become less universal by a factor of 1.5-3 relative to the isotropic case, but remain approximately universal to 10%. We succeed in explaining this increase in variability as an increase in the eccentricity variation of isodensity contours, which provides further support for the emergent approximate symmetry explanation of universality. Anisotropy does not affect the universal relations to a sufficient level to prevent their use in gravitational wave astrophysics or in experimental relativity. We provide an explicit example of the latter in dynamical Chern-Simons gravity. The increase in variability of the universal relations due to pressure anisotropy could affect their use in future X-ray observations. Given expected observational uncertainties, however, the relations remain sufficiently universal for use in such observations if the anisotropic modifications to the moment of inertia and the quadrupole moment are less than 10% of their isotropic values.

Effect of an arbitrary spin orientation on the quadrupolar structure of an extended body in a Schwarzschild spacetime

The influence of an arbitrary spin orientation on the quadrupolar structure of an extended body moving in a Schwarzschild spacetime is investigated. The body dynamics is described by the Mathisson-Papapetrou-Dixon model, without any restriction on the motion or simplifying assumption on the associated spin vector and quadrupole tensor, generalizing previous works. The equations of motion are solved analytically in the limit of small values of the characteristic length scales associated with the spin and quadrupole variables with respect to the characteristic length of the background curvature. The solution provides all corrections to the circular geodesic on the equatorial plane taken as the reference trajectory due to both the dipolar and quadrupolar structures of the body as well as the conditions which the nonvanishing components of the quadrupole tensor must fulfill in order for the problem to be self-consistent.

25mg NMR Studies of Mg-Ion Battery Materials

Multivalent-ion chemistries such as Mg-ion are emerging as alternative battery systems to Li-ion. Current Mg-ion chemistries are limited to relatively low voltages and relatively low reversible specific capacities (1-2). Recent research on potential high voltage Mg-ion cathode materials and alternative anode materials such as transition metal oxides and metal alloys have highlighted the urgent need to understand structure activity relationships and insertion/intercalation phenomenon for development of such systems (3). Solid state NMR is a powerful tool to investigate local structure and insertion/intercalation phenomena, particularly for batteries as shown for Li-ion chemistries with 6Li and 7Li NMR (4, 5). However, the low natural abundance (10%) of the NMR active Mg isotope (25Mg), highly quadrupolar nuclear spin of 25Mg (spin 5/2) and very low gyromagnetic ratio (i.e 30.6 MHz Larmor frequency relative to 1H = 500 MHz) limits the effective use of 25Mg NMR for solid Mg-ion battery materials (6). In this work, despite the challenges of 25Mg NMR, our recent efforts to characterize Mg environments in cathode materials such as MgMn2O4 spinels, MgV2O5, in anode materials such as h-TiO2 and Mg-Sn alloys will be presented. Chemical magnesiation using dibutylmagnesium and preliminary electrochemical (de)mangesiation and the structral changes induced will be discussed. The results will summarize the effectiveness of the method in distinguishing side reactions or undesirable conversion reactions, including amorphous phases, from intercalation phenomenon.

NiFe2O4 nanorod: porosity effect on spin canting, quadrupole splitting and hyperfine magnetic properties

Porous nickel ferrite nanorods having diameter ∼200 nm and length ∼2.5 to 3.0 μm were synthesized by microemulsion method followed by calcination at 450 °C. The morphology and structure of the final as well as intermediate materials, formed during this method, were characterized by x-ray diffraction, field emission scanning electron microscope, high resolution transmission electron microscope and Fourier transform infrared spectroscopy. Positron annihilation spectroscopy was used to identify the structural defects such as vacancies and surface disorder, and to find out the porosity of the synthesized nanorods. Mössbauer spectroscopy was used to determine the cation distribution and magnetic hyperfine property of the nanorods. Detailed magnetic characterization by measuring magnetization as a function of magnetic field and temperature were examined by physical property measurement system and SQUID magnetometer, respectively. The reduced saturation magnetization (Ms = 20.3 emu gm−1) and enhanced coercive (Hc = 37 Oe) field of our synthesized samples was explained on the basis of surface electron effect. Moreover, formation mechanism and effect of precursor materials were also discussed.

Effects of magnetic anisotropy on spin dynamics of ferromagnetic frustrated chain

By exploiting density-matrix renormalization group techniques, we investigate the spin dynamics of a spin-1/2 one-dimensional J1-J2 XXZ model with competing ferromagnetic J1 and antiferromagnetic J2 exchange couplings under applied magnetic fields. Numerical results of spin excitation spectra show that in the field-induced spin quadrupole regime, the longitudinal component has a gapless mode and the transverse component has a gapped mode irrespective of the exchange anisotropy. The excitation gap of the transverse spin excitation increases as the exchange anisotropy increases over the XY-like and Ising-like regions, demonstrating that two-magnon bound states are stabilized due to the easy-axis anisotropy.

Mimic of the green fluorescent protein β-barrel: photophysics and dynamics of confined chromophores defined by a rigid porous scaffold.

Chromophores with a benzylidene imidazolidinone core define the emission profile of commonly used biomarkers such as the green fluorescent protein (GFP) and its analogues. In this communication, artificially engineered porous scaffolds have been shown to mimic the protein β-barrel structure, maintaining green fluorescence response and conformational rigidity of GFP-like chromophores. In particular, we demonstrated that the emission maximum in our artificial scaffolds is similar to those observed in the spectra of the natural GFP-based systems. To correlate the fluorescence response with a structure and perform a comprehensive analysis of the prepared photoluminescent scaffolds, (13)C cross-polarization magic angle spinning solid-state (CP-MAS) NMR spectroscopy, powder and single-crystal X-ray diffraction, and time-resolved fluorescence spectroscopy were employed. Quadrupolar spin-echo solid-state (2)H NMR spectroscopy, in combination with theoretical calculations, was implemented to probe low-frequency vibrational dynamics of the confined chromophores, demonstrating conformational restrictions imposed on the coordinatively trapped chromophores. Because of possible tunability of the introduced scaffolds, these studies could foreshadow utilization of the presented approach toward directing a fluorescence response in artificial GFP mimics, modulating a protein microenvironment, and controlling nonradiative pathways through chromophore dynamics.

Entangled tetrahedron ground state and excitations of the magnetoelectric skyrmion materialCu2OSeO3

The strongly correlated cuprate Cu$_2$OSeO$_3$ has recently been identified as the first insulating system exhibiting a skyrmion lattice phase. Using a microscopic multi-boson theory for its magnetic ground state and excitations, we establish the presence of two distinct types of modes: a low energy manifold that includes a gapless Goldstone mode and a set of weakly dispersive high-energy magnons. These spectral features are the most direct signatures of the fact that the essential magnetic building blocks of Cu$_2$OSeO$_3$ are not individual Cu spins, but rather weakly-coupled Cu$_4$ tetrahedra. Several of the calculated excitation energies are in nearly perfect agreement with reported Raman and far-infrared absorption data, while the magneto-electric effect determined within the present quantum-mechanical framework is also fully consistent with experiments, giving strong evidence in the entangled Cu$_4$ tetrahedra picture of Cu$_2$OSeO$_3$. The predicted dispersions along with the dynamical dipole and quadrupole spin structure factors call for further experimental tests of this picture.

Nuclear spin scissors – new type of collective motion

The coupled dynamics of the orbital and spin scissors modes is studied with the help of the Wigner Function Moments method on the basis of Time Dependent Hartree-Fock equations in the harmonic oscillator model including spin orbit potential plus quadrupole- quadrupole and spin-spin residual interactions. The relation between our results and the recent experimental data is discussed.

AFNMR/NQR signal enhancement via population transfer

Antiferromagnetic nuclear magnetic resonance (AFNMR) and nuclear quadrupole resonance (NQR) are useful techniques to characterize materials in bulk volumes without applying external static magnetic fields. For industrial materials characterization applications, it is crucial to maximize signal‐to‐noise ratio in the available time. We simulate the AFNMR and NQR signal enhancement via population transfer in single crystals and powders and predict the enhancement factors for half‐integer quadrupolar nuclei spin systems. Differences to conventional high‐field NMR population transfer experiments are emphasized. We restrict our discussion to electric field gradients with axial symmetry = 0. Triple resonance tuned crossed coil experiments on CuFeS2 and In2O3 powders support the numerical results. © 2015 Wiley Periodicals, Inc. Concepts Magn Reson Part A 43A: 147–156, 2015.

Manipulation of the nuclear spin ensemble in a quantum dot with chirped magnetic resonance pulses.

The nuclear spins in nanostructured semiconductors play a central role in quantum applications. The nuclear spins represent a useful resource for generating local magnetic fields but nuclear spin noise represents a major source of dephasing for spin qubits. Controlling the nuclear spins enhances the resource while suppressing the noise. NMR techniques are challenging: the group III and V isotopes have large spins with widely different gyromagnetic ratios; in strained material there are large atom-dependent quadrupole shifts; and nanoscale NMR is hard to detect. We report NMR on 100,000 nuclear spins of a quantum dot using chirped radiofrequency pulses. Following polarization, we demonstrate a reversal of the nuclear spin. We can flip the nuclear spin back and forth a hundred times. We demonstrate that chirped NMR is a powerful way of determining the chemical composition, the initial nuclear spin temperatures and quadrupole frequency distributions for all the main isotopes. The key observation is a plateau in the NMR signal as a function of sweep rate: we achieve inversion at the first quantum transition for all isotopes simultaneously. These experiments represent a generic technique for manipulating nanoscale inhomogeneous nuclear spin ensembles and open the way to probe the coherence of such mesoscopic systems.

Single Crystal Solid-State NMR of Magnetically Oriented Powder

Solid-state NMR spectroscopy is one of the most widely used methods for investigating crystal structures, along with the X-ray and neutron diffraction methods. Solid-state NMR can provide structural information including isotropic chemical shift, dipolar and quadrupolar couplings, spin diffusion, and chemical shift tensor. Among these, the chemical shift tensor is of particular significance because the electronic environment around a nucleus is directly reflected on the chemical shift tensor. However, full information of the chemical shift tensor, including principal values and axes, is difficult to obtain experimentally because a large single crystal is required for the measurement. On the other hand, we have proposed the use of a magnetically oriented microcrystal array (MOMA) as an alternative to a single crystal.[1,2] A MOMA is a composite in which microcrystals are aligned three-dimensionally, prepared by using a time-dependent magnetic field. We recently demonstrated that the13C chemical shift tensors of L-alanine crystal can be completely determined by application of the standard procedure in the single-crystal rotation method to a MOMA of L-alanine microcrystals,[3] as shown in Figure 1. The L-alanine MOMA produces sharp resonance peaks without resolution enhancement by magic angle spinning (MAS). In addition, we observed that the positions of the13C resonance peaks vary systematically as a function of the angle ψ that is the sample-rotation angle about the axis inclined by the magic angle with respect to the NMR magnetic field. From the ψ-dependence of the chemical shifts,13C chemical shift tensor was completely determined. We confirmed that the combination of MOMA with the single-crystal rotation method can be applied to other nuclei such as31P and15N. These results clearly show that the MOMA method is a powerful tool for obtaining full information of the chemical shift tensor from a microcrystalline powder without MAS.

ChemInform Abstract: The D‐HMQC MAS‐NMR Technique: An Efficient Tool for the Editing of Through‐Space Correlation Spectra Between Quadrupolar and Spin‐1/2 (31P, 29Si, 1H, 13C) Nuclei.

The D-HMQC (dipolar heteronuclear multiple-quantum coherence) technique is a recently developed NMR pulse sequence particularly suitable for the investigation of spatial proximity between quadrupolar and spin-1/2 nuclei. Compared to the cross-polarisation magic-angle spinning technique applied to a quadrupolar nucleus, D-HMQC does not require time-consuming optimisations and exhibits on the quadrupolar spin a better robustness to irradiation offset and to Cq values and radiofrequency field. Furthermore, the high robustness to irradiation offset makes of the D-HMQC sequence the technique of choice for the structural characterisation of materials especially at high magnetic field. We show here how the D-HMQC can be easily implemented and optimised to give access to the structural analysis of silicate-, phosphate-, carbon- and proton-containing materials. An emphasis will be on describing the most popular dipolar recoupling schemes that can be used in that sequence and providing their advantages and drawbacks.

ChemInform Abstract: Distance Measurements to Metal Ions and Other Quadrupolar Spins by Magic Angle Spinning Solid State NMR

AbstractReview: 82 refs.

Phase-modulated LA-REDOR: A robust, accurate and efficient solid-state NMR technique for distance measurements between a spin-1/2 and a quadrupole spin

Distances between a spin-1/2 and a spin>1/2 can be efficiently measured by a variety of magic-angle spinning solid state NMR methods such as Rotational Echo Adiabatic Passage Double Resonance (REAPDOR), Low-Alpha/Low-Amplitude REDOR (LA-REDOR) and Rotational-Echo Saturation-Pulse Double-Resonance (R/S-RESPDOR). In this manuscript we show that the incorporation of a phase modulation into a long quadrupolar recoupling pulse, lasting 10 rotor periods that are sandwiched between rotor-synchronized pairs of dipolar recoupling π pulses, extends significantly the range of the values of the quadrupole moments that can be accessed by the experiment. We show by a combination of simulations and experiments that the new method, phase-modulated LA-REDOR, is very weakly dependent on the actual value of the radio-frequency field, and is highly robust with respect to off-resonance irradiation. The experimental results can be fitted by numerical simulations or using a universal formula corresponding to an equal-transition-probability model. Phase-modulated LA-REDOR 13C{11B} and 15N{51V} dipolar recoupling experiments confirm the accuracy and applicability of this new method.