Dipolar Coupling Research Articles

Dual physical stimuli fluorescence response of an α-cyanostilbene derivative for dynamic information storage

α-cyanostilbene derivatives, known as AIE molecules, have the potential to serve as optical recorders and vapor sensor by altering the molecular aggregation and / or stacking models. Despite the significant scientific and technological importance of the correlation between molecular stacking modes and modulated optical properties, relevant research remains scarce. Herein, two thermodynamically stable crystalline phase (BCr and GCr) were found for a biphenyl-based cyanostilbenic compound, DSB-SQ, condensed from its solution. Uniquely, the BCr demonstrated reversible mechanochromism and irreversible thermalchromism, whereas GCr remained unaffected by exposure to light, heat, grinding, etc. The discoloration process was correlated with the variation of local dipole coupling modes during the phase transition, leading to a significant change in π-π overlap and delocalization of excited states. Finally, the BCr was doped with polyvinyl alcohol (PVA) to prepare a composite membrane with dynamic information storage and encryption function.

Excitation of exchange spin waves in a magnetic insulator thin film at cryogenic temperatures

Spin waves and their quanta, magnons, are promising candidates for next-generation electronic devices, due to their low-power consumption and compatibility with radio-frequency-based electronic devices. For achieving magnon-based hybrid quantum systems for quantum memory and computation, the investigation of spin-wave propagation at cryogenic temperatures is highly required. In this article, we report the excitation and detection of exchange spin waves with wavelengths of tens of nanometers in an yttrium iron garnet (YIG) thin film at cryogenic temperatures. We find that the exchange spin waves are unidirectional in all temperature ranges, owing to the chiral dynamical dipolar coupling between the spin-wave mode in the YIG and the ferromagnetic resonance mode in the cobalt nanowire. Notably, a high exchange spin-wave group velocity of 2 km s−1 at 10 K is observed. Our results are promising for the development of high-speed and energy-efficient quantum magnonic devices operating at cryogenic temperatures.

Full configurational and conformational analysis of artemisinin by one-bond carbon-carbon residual dipolar couplings at natural abundance.

Configurational and conformational analysis of the biologically relevant natural product artemisinin was conducted using carbon-carbon residual dipolar couplings (1DCC RDCs) at natural abundance. These RDCs were measured through the 2D-INADEQUATE NMR experiment using a sample aligned in a compressed poly (methyl methacrylate) (PMMA) gel swollen in CDCl3. Singular value decomposition (SVD) fitting analysis of all carbon-carbon bonds, 1DCC RDCs, in relation to the full configuration/conformational space (32 diastereoisomers) of artemisinin, unambiguously identified the correct configuration of artemisinin.

Elucidation of the Mechanisms of Inter-domain Coupling in the Monomeric State of Enzyme I by High-pressure NMR

The catalytic cycle of Enzyme I (EI), a phosphotransferase enzyme responsible for converting phosphoenolpyruvate (PEP) into pyruvate, is characterized by a series of local and global conformational rearrangements. This multistep process includes a monomer-to-dimer transition, followed by an open-to-closed rearrangement of the dimeric complex upon PEP binding. In the present study, we investigate the thermodynamics of EI dimerization using a range of high-pressure solution NMR techniques complemented by SAXS experiments. 1H-15N TROSY and 1H-13C methyl TROSY NMR spectra combined with 15N relaxation measurements revealed that a native-like engineered variant of full-length EI fully dissociates into stable monomeric state above 1.5 kbar. Conformational ensembles of EI monomeric state were generated via a recently developed protocol combining coarse-grained molecular simulations with experimental backbone residual dipolar coupling measurements. Analysis of the structural ensembles provided detailed insights into the molecular mechanisms driving formation of the catalytically competent dimeric state, and reveals that each step of EI catalytical cycle is associated with a significant reduction in either inter- or intra-domain conformational entropy. Altogether, this study completes a large body work conducted by our group on EI and establishes a comprehensive structural and dynamical description of the catalytic cycle of this prototypical multidomain, oligomeric enzyme.

Reciprocity relations in a biologically inspired nanomagnonic system with dipolar coupling

Magnetosome chains in magnetotactic bacteria present ideal nanomagnonic model systems for studying collective resonance modes of dipolar-coupled single domain particles in relation to their spatial arrangement. Using microresonator-based ferromagnetic resonance (FMR) spectroscopy, electron microscopy, and micromagnetic modeling, we here provide insights into the complex magnonic activity within a single magnetosome chain. While the angular dependence of its FMR spectrum is dominated by twofold symmetry features due to the uniaxial anisotropy of linear chain segments, we also observed an unexpected behavior such as interrupted lines and flat bands due to the intricate geometrical details of this particular chain, such as a cross-like structural anomaly where a pair of particles is oriented perpendicular to the main axis of the chain and thus breaks the prevailing axial dipolar coupling symmetry. Such a cross junction formed by four particles exhibits interesting magnonic network properties. Notably, we observe reciprocity in the sense that the spectral response of one particle to an excitation of another one is identical to the response of the latter given an excitation of the former. Furthermore, we have identified that magnonic coupling between A and B can be facilitated via a dark state, as in magnonic stimulated Raman adiabatic passage, and that this dark-state coupling can be made non-reciprocal between A and B by breaking the symmetry of the spatial arrangement of the four particles.

Precise Structural and Dynamical Details in Zeolites Revealed by Coupling-Edited 1H-17O Double Resonance NMR Spectroscopy.

Despite the extensive industrial and research interests in zeolites, their intrinsic catalytic nature is not fully understood due to the complexity of the hydroxyl-aluminum moieties. 17O NMR would provide irreplaceable opportunities for much-needed fine structural determination given the ubiquitous presence of oxygen atoms in nearly all species; however, the low sensitivity and quadrupolar nature of oxygen-17 make its NMR spectroscopic elucidation challenging. Here, we show that state-of-the-art double resonance solid-state NMR techniques have been combined with spectral editing methods based on scalar (through-bond) and dipolar (through-space) couplings, which allowed us to address the subtle protonic structures in zeolites. Notably, the often-neglected and undesired second-order quadrupolar-dipolar cross-term interaction ("2nd-QD interaction") can actually be exploited and can help gain invaluable information. Eventually, a comprehensive set of 1H-17O/1H-27Al double resonance NMR with J-/D-coupling spectral editing techniques have been designed in this work and enabled us to reveal atomic-scale precise structural and dynamical details in zeolites including: 1) The jump rate of the bridging acid site (BAS) proton is relatively low, i.e., far less than 100 s-1 at room temperature. 2) The Al-OH groups with 1H chemical shift at 2.6-2.8 ppm, at least for nonseverely dealuminated H-ZSM-5 catalysts, exhibit a rigid bridging environment similar to that of BAS. 3) The Si-OH groups at 2.0 ppm are not hydrogen bonded and undergo fast cone-rotational motion. The results in this study predict the 2nd-QD interaction to be universal for any rigid -17O-H environment, such as those in metal oxide surfaces or biomaterials.

Optical pumping of 5s4d1D2 strontium atoms for laser cooling and imaging

We present a faster repumping scheme for strontium magneto-optical traps operating on the broad 5s21S0−5s5p1P1 laser cooling transition. Contrary to existing repumping schemes, we directly address lost atoms that spontaneously decayed to the 5s4d1D2 state, sending them back into the laser cooling cycle by optical pumping on the 5s4d1D2−5s8p1P1 transition. We thus avoid the ∼100µs-slow decay path from 5s4d1D2 to the 5s5p3P1,2 states that is part of other repumping schemes. Using one low-cost external-cavity diode laser emitting at 448nm, we show our scheme increases the flux out of a 2D magneto-optical trap by 60% compared to without repumping. Furthermore, we perform spectroscopy on the 5s4d1D2−5s8p1P1 transition and measure its frequency νSr88=(668917515.3±4.0±25)MHz. We also measure the frequency shifts between the four stable isotopes of strontium and infer the specific mass and field shift factors, δνSMS88,86=−267(45)MHz and δνFS88,86=2(42)MHz. Finally, we measure the hyperfine splitting of the 5s8p1P1 state in fermionic strontium and deduce the magnetic dipole and electric quadrupole coupling coefficients A=−4(5)MHz and B=5(35)MHz. Our experimental demonstration shows that this simple and very fast scheme could improve the laser cooling and imaging performance of cold strontium atom devices, such as quantum computers based on strontium atoms in arrays of optical tweezers. Published by the American Physical Society 2024

Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization.

Photoinduced electron spin polarization (ESP) is reported in the electronic ground states of three Pt(II) complexes comprised of two S = 1/2 nitronyl nitroxide (NN) radicals attached through different length para-phenylethynyl bridges to the 3,6 positions of a catecholate (CAT, donor) and 4,4'-di-tert-butyl-2,2'-bipyridine (bpy, acceptor). Complexes 1-3 have from 17 to 41 bonds separating NN radicals and display cw-EPR spectra consistent with |JNN-NN| ≫ |aN|, |JNN-NN| ≥ |aN|, and |JNN-NN| < |aN|, respectively, where JNN-NN is the magnetic exchange coupling between NN radicals in the electronic ground state, and aN is the isotropic 14N hyperfine coupling constant. Light-induced transient EPR spectra characterized as enhanced ground-state absorption were observed for all three complexes using 532 nm pulsed laser excitation into the ligand-to-ligand charge transfer (LL'CT) band of the (CAT)Pt(bpy) chromophore. The magnitude of the observed ESP increases in the order 1 < 2 < 3 and is inversely correlated with the magnitude of ground-state JNN-NN. In addition to the experimental observation of net absorptive polarization in 1-3, light excitation also produces multiplet polarization in 2. Since the weak dipolar coupling leads to a strong spectral overlap of the absorptive and emissive components, the multiplet polarization is not observed in 1 and 3 and is very weak in 2. The ability to spin-polarize multiple radical spins with a single photon is anticipated to advance new photoinduced multi qubit/qudit ESP protocols for quantum information science applications.

The effect of magnetic field on the orientational ordering of easy magnetization axes in superparamagnetic nanoparticles

The active use of nanoparticles in modern biomedical applications and technologies requires reliable theoretical models capable of predicting physical properties. The effect of a static magnetic field on the orientational ordering of the easy magnetization axes in an ensemble of superparamagnetic nanoparticles (SNPs) is studied using a combination of statistical-mechanical theory and computer simulations. The magnetic dipole-dipole interaction between particles is taken into account within the framework of the modified mean-field approach. The alignment distributions of the easy magnetization axes of the SNPs and the static magnetic characteristics of the ferrocomposite are analyzed. The presence of even weak interparticle magneto-dipole interactions results in a notable enhancement of the magnetic susceptibility of the ferrocomposite.

Searching for exotic spin-dependent interactions with diamond-based vector magnetometer

We propose a new method to search for exotic spin-spin interactions between electrons and nucleons using a diamond-based vector magnetometer. The vector magnetometer can be constructed from ensembles of nitrogen-vacancy centers along different axes in a diamond. The N14 nuclear spins of nitrogen-vacancy centers in the same diamond can be polarized through the dynamic nuclear polarization method to serve as spin sources. With the vector magnetometer, the sought-after exotic interactions can be distinguished from the magnetic dipole-dipole interaction. For the axion-mediated interaction VPP, new upper bounds of the coupling |gPegPN| are expected within the force range from 10 nm to 100 μm. For the Z′-mediated interaction VAA, new upper bounds of the coupling |gAegAN| are expected within the force range from 10 nm to 1 cm. The new upper bounds for VPP and VAA are both expected to be more than 5 orders of magnitude more stringent than existing constraints at the force range of 1 μm with the total measurement time of 1 day. Published by the American Physical Society 2024

Magnon-Assisted Magnetization Reversal of Ni81Fe19 Nanostripes on Y3Fe5O12 with Different Interfaces.

Magnetic bit writing by short-wave magnons without conversion to the electrical domain is expected to be a game-changer for in-memory computing architectures. Recently, the reversal of nanomagnets by propagating magnons was demonstrated. However, experiments have not yet explored different wavelengths and the nonlinear excitation regime of magnons required for computational tasks. We report on the magnetization reversal of individual 20 nm thick Ni81Fe19 (Py) nanostripes integrated onto 113 nm thick yttrium iron garnet (YIG). We suppress direct interlayer exchange coupling by an intermediate layer, such as Cu and SiO2. By exciting magnons in YIG with wavelengths λ down to 148 nm we observe the reversal of the integrated ferromagnets in a small external field of 14 mT. Magnons with a small wavelength of λ = 195 nm, i.e., twice the width of the Py nanostripes, induced the reversal at a spin-precessional power of only about 1 nW after propagating over 15 μm in YIG. Such small power value has not been reported so far. Considerations based on dynamic dipolar coupling explain the observed wavelength dependence of the magnon-induced reversal efficiency. For an increased power, the stripes reversed in an external field of only about 1 mT. Our findings are important for the practical implementation of nonvolatile storage of broadband magnon signals in YIG by means of bistable nanomagnets without the need of an appreciable global magnetic field.

The 2D-IR spectrum of hydrogen-bonded silanol groups in pyrogenic silica.

Pyrogenic silica is a form of amorphous silica with a high surface area and a heterogeneous distribution of silanol hydroxyl terminations and defects. In this work, the interesting and unusual form of the hydroxyl-stretch 2D-IR spectrum of pyrogenic silica is presented and explored in the deuterated (deuteroxyl) form. Transition dipole couplings between hydrogen-bonded and non-hydrogen-bonded silanol groups give a distinct cross-peak in the 2D-IR spectrum, displaying interstate coherence oscillations during the 2D-IR experimental waiting time. The strong asymmetry about the diagonal is proposed to be the result of both the relatively small transition dipole coupling strength and the extreme differences in the width of the hydrogen-bonded and non-hydrogen-bonded silanol bands. The resulting interference of negative and positive cross-peaks has minimal intensity in the below-diagonal ω3 < ω1 region of the spectrum. An additional strong positive cross-peak is observed at a position in the 2D-IR spectrum inconsistent with transition dipole coupling. An assignment as a fifth order effect is proposed.

Investigation of magnetization dynamics in trilayer width-modulated nanowires

We have investigated the magnetization reversal processes and dynamic behavior of trilayered Py(50 nm)/Pd(tPd)/Py(20 nm) nanowires with periodic width modulation as a function of spacer layer thickness tPd in the range from 0 to 10 nm and compared them with single-layer nanowires. The ferromagnetic resonance spectra show more than three modes that result from a non-uniform demagnetizing field in width-modulated nanowires. We observe that the spacer layer thickness influenced the ferromagnetic resonance spectra, which showed different numbers and values of modes and frequencies due to the different magnetization configurations for different spacer layer thicknesses. We also found that the two ferromagnetic layers are exchange-coupled for tPd = 2 nm nanowire arrays, showing the sharp switching of magnetization from the static measurements and sharp frequency jump from 13.6 to 14.7 GHz around −18 mT from the dynamic measurements. However, for tPd = 10 nm, the two layers switch at different fields, indicating a gradual decrease in magnetization as the reversal is mediated through dipolar coupling. The origin of modes is well explained from the spatial mode profiles of top and bottom magnetic layers. The dynamic responses in this spin-valve-type structure are useful for designing microwave-based spintronic devices.

Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets.

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4fn systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT(μ-Me)(THF)]2 (2) and the nearly linear Li[(ErCOT)2(μ-Me)3] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT(Bn)(THF)2 (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin-vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased.

Quantum Drude oscillators coupled with Coulomb potential as an efficient model for bonded and non-covalent interactions in atomic dimers.

The quantum Drude oscillator (QDO) model has been widely used as an efficient surrogate to describe the electric response properties of matter as well as long-range interactions in molecules and materials. Most commonly, QDOs are coupled within the dipole approximation so that the Hamiltonian can be exactly diagonalized, which forms the basis for the many-body dispersion method [Phys. Rev. Lett. 108, 236402 (2012)]. The dipole coupling is efficient and allows us to study non-covalent many-body effects in systems with thousands of atoms. However, there are two limitations: (i) the need to regularize the interaction at short distances with empirical damping functions and (ii) the lack of multipolar effects in the coupling potential. In this work, we convincingly address both limitations of the dipole-coupled QDO model by presenting a numerically exact solution of the Coulomb-coupled QDO model by means of quantum Monte Carlo methods. We calculate the potential-energy surfaces of homogeneous QDO dimers, analyzing their properties as a function of the three tunable parameters: frequency, reduced mass, and charge. We study the coupled-QDO model behavior at short distances and show how to parameterize this model to enable an effective description of chemical bonds, such as the covalent bond in the H2 molecule.

Large dynamics of a phase separating arginine-glycine-rich domain revealed via nuclear and electron spins

Liquid-liquid phase separation is the key process underlying formation of membrane-less compartments in cells. A highly dynamic cellular body with rapid component exchange is Cajal body (CB), which supports the extensive compositional dynamics of the RNA splicing machinery, spliceosome. Here, we select an arginine-glycine (RG)-rich segment of coilin, the major component of CB, establish its RNA-induced phase separation, and through combined use of nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) probes, interrogate its dynamics within the crowded interior of formed droplets. Taking advantage of glycine-based singlet-states, we show that glycines retain a large level of sub-nanoseconds dynamics inside the coilin droplets. Furthermore, the continuous-wave (CW) and electron-electron dipolar (PELDOR) and electron-nucleus hyperfine coupling EPR data (HYSCORE) support the RNA-induced formation of dynamic coilin droplets with high coilin peptide concentrations. The combined NMR and EPR data reveal the high dynamics of the RG-rich coilin within droplets and suggest its potential role in the large dynamics of CBs.

Role of Protons in and around Strongly Coupled Nitroxide Biradicals for Cross-Effect Dynamic Nuclear Polarization.

In magic angle spinning dynamic nuclear polarization (DNP), biradicals such as bis-nitroxides are used to hyperpolarize protons under microwave irradiation through the cross-effect mechanism. This mechanism relies on electron-electron spin interactions (dipolar coupling and exchange interaction) and electron-nuclear spin interactions (hyperfine coupling) to hyperpolarize the protons surrounding the biradical. This hyperpolarization is then transferred to the bulk sample via nuclear spin diffusion. However, the involvement of the protons in the biradical in the cross-effect DNP process has been under debate. In this work, we address this question by exploring the hyperpolarization pathways in and around bis-nitroxides. We demonstrate that for biradicals with strong electron-electron interactions, as in the case of the AsymPols, the protons on the biradical may not be necessary to quickly generate hyperpolarization. Instead, such biradicals can efficiently, and directly, polarize the surrounding protons of the solvent. The findings should impact the design of the next generation of biradicals.

Evaluation of Copper(II) Transfer between Amyloid-beta Peptides by Relaxation-Induced Dipolar Modulation Enhancement (RIDME).

In the brains of Alzheimer's disease patients, fibrillar aggregates containing amyloid-beta (Aβ) peptides are found, along with elevated concentrations of Cu(II) ions. The aggregation pathways of Aβ peptides can be modulated by Cu(II) ions and is determined by the formation and nature of the Cu(II)-Aβ complex. If spin-labeled, the Cu(II)-Aβ complex contains two dipolar coupled paramagnetic centers, the spin label and the Cu(II) ion. Measurement of the dipolar coupling between these paramagnetic centers by relaxation-induced dipolar modulation enhancement (RIDME) allows to monitor the complex formation and thus opens a way to follow the Cu(II) transfer between peptides if a mixture of wild-type and spin-labeled ones is used. We evaluate this approach for a specific Cu(II)-Aβ complex, the aggregation-inert Component II. The kinetics of the Cu(II) transfer can be resolved by performing RIDME in a time-dependent manner. A temporal resolution of seconds has been achieved, with the potential to reach milliseconds, using a rapid-freeze quench device to stop the Cu(II) transfer in solution after defined incubation times.

Sub-10 nm magnetic sensor for gigahertz operation using lateral spin valve structure

We present a new magnetic sensor design using a lateral spin valve (LSV) structure that features a sensing end less than 10 nm thick, making it suitable for integration with nanoscale devices. Shot noise reduction and signal-to-noise ratio (SNR) improvement under gigahertz operation are expected for our design. The spin detection part of the LSV forms a magnetic tunnel junction (MTJ) beneath the aluminum channel. We propose to replace the single layer ferromagnet in the spin detection part of the LSV with a synthetic antiferromagnetic structure: this facilitates spin-transfer torque (STT) induced magnetization switching. Macrospin simulation shows that interlayer magnetic dipole coupling helps STT switching while interlayer exchange coupling hurts, owing to their different precession symmetries in the out-of-plane direction. It also shows that SNR > 20 dB can be achieved for a pseudorandom binary sequence with a minimum bit length 0.5 ns.

Dipole Coupling Accelerated H2 O Dissociation by Magnesium-Based Intermetallic Catalysts.

The water (H2 O) dissociation is critical for various H2 O-associated reactions, including water gas shift, hydrogen evolution reaction and hydrolysis corrosion. While the d-band center concept offers a catalyst design guideline for H2 O activation, it cannot be applied to intermetallic or main group elements-based systems because Coulomb interaction was not considered. Herein, using hydrolysis corrosion of Mg as an example, we illustrate the critical role of the dipole of the intermetallic catalysts for H2 O dissociation. The H2 O dissociation kinetics can be enhanced using Mgx Mey (Me=Co, Ni, Cu, Si and Al) as catalysts, and the hydrogen generation rate of Mg2 Ni-loaded Mg reached 80 times as high as Ni-loaded Mg. The adsorbed H2 O molecules strongly couple with the Mg-Me dipole of Mgx Mey , lowering the H2 O dissociation barrier. The dipole-based H2 O dissociation mechanism is applicable to non-transition metal-based systems, such as Mg2 Si and Mg17 Al12 , offering a flexible catalyst design strategy for controllable H2 O dissociation.