Nuclear Spin Coupling Research Articles

Optimizing noble gas pressure for enhanced self-compensation in spin-exchange relaxation-free comagnetometers.

The coupling of electron spin and nuclear spin through spin-exchange collisions compensates for external magnetic field interference in the spin-exchange relaxation-free (SERF) comagnetometer. However, the compensation ability for magnetic field interference along the detection axis is limited due to the presence of nuclear spin relaxation. This paper aims to enhance the self-compensation capability of the system by optimizing the pressure of the noble gas during cell filling. Models are established to describe the relationships between the nuclear spin polarization, the polarizing magnetic field of nuclei, the magnetic field suppression factors, and the pressure of the noble gas in the K-Rb-21Ne atomic ensemble. Experiments are conducted using five cells with different pressure. The results indicate that in the positive pressure area, the nuclear spin polarization decreases while the equivalent magnetic field experienced by the noble gas increases with increasing pressure. The magnetic field suppression factor for transverse fields increases as the pressure increases, leading to a decrease in the ability to suppress low-frequency magnetic field interference. Moreover, at the cell temperature of 180°C and a transverse residual field gradient of 4.012 nT/cm, the system exhibits its strongest capability to suppress transverse magnetic field interference when the pressure of 21Ne is around 0.7 atm.

Indirect Nuclear Spin-Spin Exchange Coupling through Solvated Electron in Small Sizes of Cyclic and Cage-Shaped Perfluoroalkanes.

Small perfluorocycloalkanes (hexafluorocyclopropane (c-C3 F6 ), octafluorocyclobutane (c-C4 F8 ) and decafluorocyclopentane (c-C5 F10 ) and cage-shaped perfluoroalkanes (perfluoro tetrahedral alkane (C4 F4 ), perfluoro prismane (C6 F6 ) and perfluoro cubane (C8 F8 )) are better electron scavengers. The captured excess electrons are weakly bound inside their backbone voids or over their backbones, forming the solvated electron ( ) systems (e@c-Cn F2n s (n=3, 4, 5) and e@Cn Fn (n=4, 6, 8)). There have been many studies on the structures and properties of such systems. However, the effect of on the indirect nuclear spin-spin coupling (J-coupling) is unknown. In this work, we explore how affects Ne J-coupling between two coupled F nuclei (Ne JFF -coupling) in perfluoroalkane systems through density functional theory calculations. We find unusual trans-Ne JFF -couplings (two coupled F nuclei in trans-position) in e@c-Cn F2n (n=3, 4, 5) and Ne JFF -couplings in e@Cn Fn (n=4, 6, 8). One excess electron not only changes the molecular structures, but also enforces unique distributions and properties, depending on the structural characteristics. We also confirm that such unusual Ne JFF -couplings are realized by through- (T-SE) transmission mechanism, rather than the conventional through-bonds (T-B)/through-space (T-S) ones. The novel transmission mechanism consists of the T-SE coupling path (path 1) and -enhanced T-B T-S coupling path (path 2), and the two paths jointly control Ne JFF through cooperation and competition. Interestingly, the former plays a dominant role for long-range Ne JFF -coupling (N=5), while the latter plays a role in the short-range Ne JFF -coupling (N=3, 4). Path bending angle mainly influences path 1, while path 2 is mainly influenced by the path length. This work not only provides novel insights into the mediating role of in the coupling information exchange, but also proposes a new -based coupling mechanism, possibly opening up potential applications for the -based indirect nuclear spin couplings.

Atomic-Scale Quantum Sensing of Ensembles of Guest Molecules in a Metal-Organic Framework with Intrinsic Electron Spin Centers.

One of the exciting applications of electron-spin-based quantum sensing is the detection of distant nuclear spins of external molecular species. Here, we explore the application of a metal-organic framework (MOF) material as a host matrix for sensing spin centers. As a sensor, we employ inherent Cu2+ ions in the structure of a Zn-doped HKUST-1 framework. As a target molecular species, we use butane gas that exhibits no specific chemical reactivity toward the inner surface of HKUST-1 and is thus randomly distributed inside the MOF pore network. By employing a conventional double-resonance pulse sequence, we can effectively detect the coupling of the distant 1H nuclear spins of butane to the electron spin of the sensor and gain atomic-scale insight into their spatial distribution. Thus, our proof-of-the-concept experiment demonstrates that MOFs, the materials featuring extremely large surface area and great tunability, are perfectly suited as a key element for emerging magnetic quantum sensing solutions.

Enhanced Coupling of Electron and Nuclear Spins by Quantum Tunneling Resonances.

Noble-gas spins feature hours-long coherence times, owing to their great isolation from the environment, and find practical usage in various applications. However, this isolation leads to extremely slow preparation times, relying on weak spin transfer from an electron-spin ensemble. Here we propose a controllable mechanism to enhance this transfer rate. We analyze the spin dynamics of helium-3 atoms with hot, optically excited potassium atoms and reveal the formation of quasibound states in resonant binary collisions. We find a resonant enhancement of the spin-exchange cross section by up to 6 orders of magnitude and 2 orders of magnitude enhancement for the thermally averaged, polarization rate coefficient. We further examine the effect for various other noble gases and find that the enhancement is universal. We outline feasible conditions under which the enhancement may be experimentally observed and practically utilized.

Coherent microwave control of a nuclear spin ensemble at room temperature

We use nominally forbidden electron-nuclear spin transitions in nitrogen-vacancy (NV) centers in diamond to demonstrate coherent manipulation of a nuclear spin ensemble using microwave fields at room temperature. We show that employing an off-axis magnetic field with a modest amplitude($\approx$ 0.01 T) at an angle with respect to the NV natural quantization axes is enough to tilt the direction of the electronic spins, and enable efficient spin exchange with the nitrogen nuclei of the NV center. We could then demonstrate fast Rabi oscillations on electron-nuclear spin exchanging transitions, coherent population trapping and polarization of nuclear spin ensembles in the microwave regime. Coupling many electronic spins of NV centers to their intrinsic nuclei offers full scalability with respect to the number of controllable spins and provides prospects for transduction. In particular, the technique could be applied to long-lived storage of microwave photons and to the coupling of nuclear spins to mechanical oscillators in the resolved sideband regime.

Field-induced oscillation of magnetization blocking barrier in a holmium metallacrown single-molecule magnet

<h2>Summary</h2> Single-molecule magnets (SMMs) exhibit magnetization blocking in the presence of strong magnetic anisotropy. By employing molecular engineering, the blocking barrier can be significantly modified, remaining independent from other external factors, such as magnetic field. Taking advantage of hyperfine coupling of electronic and nuclear spins further highlights their unique functionality. However, a poor understanding of relaxation mechanisms limits the exploitation of nuclear-spin molecular qubits. Here, we report the first observation of field-dependent oscillation of the magnetization blocking barrier in a holmium metallacrown magnet driven by the switch of relaxation mechanisms involving hyperfine interaction. First-principles calculations reveal an activated temperature dependence of magnetic relaxation, dominated either by incoherent quantum tunneling of magnetization at anti-crossing points or by Orbach-like processes at crossing points. This mechanism demonstrates that these relaxation barriers can be consecutively switched by increasing the external field, which paves a way for manipulating magnetization dynamics of SMMs using hyperfine interaction.

Surprising absence of strong homonuclear coupling at low magnetic field explored by two-field nuclear magnetic resonance spectroscopy.

Strong coupling of nuclear spins, which is achieved when their scalar coupling is greater than or comparable to the difference in their Larmor precession frequencies in an external magnetic field, gives rise to efficient coherent longitudinal polarization transfer. The strong coupling regime can be achieved when the external magnetic field is sufficiently low, as is reduced proportional to the field strength. In the present work, however, we demonstrate that in heteronuclear spin systems these simple arguments may not hold, since heteronuclear spin-spin interactions alter the value. The experimental method that we use is two-field nuclear magnetic resonance (NMR), exploiting sample shuttling between the high field, at which NMR spectra are acquired, and the low field, where strong couplings are expected and at which NMR pulses can be applied to affect the spin dynamics. By using this technique, we generate zero-quantum spin coherences by means of a nonadiabatic passage through a level anticrossing and study their evolution at the low field. Such zero-quantum coherences mediate the polarization transfer under strong coupling conditions. Experiments performed with a -labeled amino acid clearly show that the coherent polarization transfer at the low field is pronounced in the spin subsystem under proton decoupling. However, in the absence of proton decoupling, polarization transfer by coherent processes is dramatically reduced, demonstrating that heteronuclear spin-spin interactions suppress the strong coupling regime, even when the external field is low. A theoretical model is presented, which can model the reported experimental results.

The Effect of Nuclear-Quadrupole Coupling in the Laser-Induced Alignment of Molecules.

We present a theoretical study of the time-dependent laser alignment of molecules taking into account the hyperfine coupling due to nuclear-quadrupole interactions. The coupling of nuclear spins to the overall angular momentum of molecules significantly influences their rotational dynamics. Here, we systematically analyze the impact of the nuclear-quadrupole coupling on the rotational dynamics of the linear and the asymmetric-top diiodobenzene molecule induced by external laser fields. We explore different regimes of pulse shapes and laser-pulse intensities and detail under which conditions the quadrupole coupling cannot be neglected in the description of the laser alignment of molecules.

Highly Reactive CoIII,IV2(μ-O)2 Diamond Core Complex That Cleaves C-H Bonds.

The selective activation of strong sp3 C-H bonds at mild conditions is a key step in many biological and synthetic transformations and an unsolved challenge for synthetic chemists. In nature, soluble methane monooxygenase (sMMO) is one representative example of nonheme dinuclear iron-dependent enzymes that activate strong sp3 C-H bonds by a high-valent diiron(IV) intermediate Q. To date, synthetic model complexes of sMMO-Q have shown limited abilities to oxidize strong C-H bonds. In this work, we generated a high-valent CoIII,IV2(μ-O)2 complex 3 supported by a tetradentate tris(2-pyridylmethyl)amine (TPA) ligand via one-electron oxidation of its CoIII2(μ-O)2 precursor 2. Characterization of 2 and 3 using X-ray absorption spectroscopy and DFT calculations showed that both species possess a diamond core structure with a short Co···Co distance of 2.78 Å. Furthermore, 3 is an EPR active species showing an S = 1/2 signal with clearly observable hyperfine splittings originated from the coupling of the 59Co nuclear spin with the electronic spin. Importantly, 3 is a highly reactive oxidant for sp3 C-H bonds, and an oxygenation reagent. 3 has the highest rate constant (1.5 M-1 s-1 at -60 °C) for oxidizing 9,10-dihydroanthracene (DHA) compared to diamond core complexes of other first-row transition metals including Mn, Fe and Cu reported previously. Specifically, 3 is about 4-5 orders of magnitude more reactive than the diiron analogs FeIII,IV2(μ-O)2 and FeIV2(μ-O)2 supported by TPA and related ligands. These findings shed light on future development of more reactive approaches for C-H bond activation by bioinspired dicobalt complexes.

A quantum many body model for the embedded electron spin decoherence in organic solids.

We present a generalized nuclear spin bath model for embedded electron spin decoherence in organic solids at low temperatures, which takes the crucial influence from hindered methyl group rotation tunneling into account. This new, quantum many body model, after resolved using the cluster correlation expansion method, predicts the decoherence profiles directly from the proton relative position and methyl group tunneling splitting inputs. Decoherence profiles from this model explain adequately the influence from both strongly and weakly hindered methyl groups to embedded electron spin decoherence: The former accelerates decoherence by increasing the nearest neighbor nuclear spin coupling, while the latter enhances coherence through a novel confinement like' mechanism, in which the very strong nuclear spin coupling from the tunneling splitting term suppresses those protons on the methyl rotors from participating in the bath dynamics. Both types of influences are successfully proven experimentally in representative organic polycrystalline matrices: methyl malonic acid for strongly hindered and acetamide for weakly hindered methyl groups, respectively.

Search for Axionlike Dark Matter with a Liquid-State Nuclear Spin Comagnetometer

We report the results of a search for axionlike dark matter using nuclear magnetic resonance (NMR) techniques. This search is part of the multifaceted Cosmic Axion Spin Precession Experiment program. In order to distinguish axionlike dark matter from magnetic fields, we employ a comagnetometry scheme measuring ultralow-field NMR signals involving two different nuclei (^{13}C and ^{1}H) in a liquid-state sample of acetonitrile-2-^{13}C (^{13}CH_{3}CN). No axionlike dark matter signal was detected above the background. This result constrains the parameter space describing the coupling of the gradient of the axionlike dark matter field to nucleons to be g_{aNN}<6×10^{-5} GeV^{-1} (95%confidence level) for particle masses ranging from 10^{-22} eV to 1.3×10^{-17} eV, improving over previous laboratory limits for masses below 10^{-21} eV. The result also constrains the coupling of nuclear spins to the gradient of the square of the axionlike dark matter field, improving over astrophysical limits by orders of magnitude over the entire range of particle masses probed.

Laser-stimulated electric quadrupole transitions in the molecular hydrogen ion H2+

Molecular hydrogen ions are of metrological relevance due to the possibility of precise theoretical evaluation of their spectrum and of external-field-induced shifts. We report the results of the calculations of the rate of laser-induced electric quadrupole transitions between a large set of ro-vibrational states of ${\rm H_2^+}$. The hyperfine and Zeeman structure of the E2 transition spectrum and the effects of the laser polarization are treated in detail. We also present the nuclear spin-electron spin coupling constants, computed with a precision 10 times higher than previously.

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters.

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C2v symmetry with a significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 s-1).

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment.

A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e- to 16e- gold centers coexist. In such complexes, nonbonded ("through-space") 31P-31P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.

Hyperfine coupling of hole and nuclear spins in symmetric (111)-grown GaAs quantum dots

In self assembled III-V semiconductor quantum dots, valence holes have longer spin coherence times than the conduction electrons, due to their weaker coupling to nuclear spin bath fluctuations. Prolonging hole spin stability relies on a better understanding of the hole to nuclear spin hyperfine coupling which we address both in experiment and theory in the symmetric (111) GaAs/AlGaAs droplet dots. In magnetic fields applied along the growth axis, we create a strong nuclear spin polarization detected through the positively charged trion X$^+$ Zeeman and Overhauser splittings. The observation of four clearly resolved photoluminescence lines - a unique property of the (111) nanosystems - allows us to measure separately the electron and hole contribution to the Overhauser shift. The hyperfine interaction for holes is found to be about five times weaker than that for electrons. Our theory shows that this ratio depends not only on intrinsic material properties but also on the dot shape and carrier confinement through the heavy-hole mixing, an opportunity for engineering the hole-nuclear spin interaction by tuning dot size and shape.

Role of the electron spin in determining the coherence of the nuclear spins in a quantum dot.

A huge effort is underway to develop semiconductor nanostructures as low-noise qubits. A key source of dephasing for an electron spin qubit in GaAs and in naturally occurring Si is the nuclear spin bath. The electron spin is coupled to each nuclear spin by the hyperfine interaction. The same interaction also couples two remote nuclear spins via a common coupling to the delocalized electron. It has been suggested that this interaction limits both electron and nuclear spin coherence, but experimental proof is lacking. We show that the nuclear spin decoherence time decreases by two orders of magnitude on occupying an empty quantum dot with a single electron, recovering to its original value for two electrons. In the case of one electron, agreement with a model calculation verifies the hypothesis of an electron-mediated nuclear spin-nuclear spin coupling. The results establish a framework to understand the main features of this complex interaction in semiconductor nanostructures.

Influence of Coupling of the Angular Momentum and Nuclear Spin on Resonance Fluorescence Polarization

Resonance fluorescence polarization for rotational transitions allowed by selection rules was calculated considering coupling of total nuclear spin from zero to five with the molecular angular momentum. It was shown that the level hyperfine structure of almost all rotational transitions led to strong depolarizing effects. The limiting anisotropy and degree of circularity were especially strongly reduced for small angular momentum quantum numbers up to the total nuclear moment of the molecule. This applied to both positive and negative values of the anisotropy and degree of circularity.

Three-stage decoherence dynamics of an electron spin qubit in an optically active quantum dot

The control of discrete quantum states in solids and their use for quantum information processing is complicated by the lack of a detailed understanding of the mechanisms responsible for qubit decoherences. For spin qubits in semiconductor quantum dots, phenomenological models of decoherence currently recognize two Basic stages; fast ensemble dephasing due to the coherent precession of spin qubits around nearly static but randomly distributed hyperfine fields and a much slower process of irreversible relaxation of spin qubit polarization due to dynamics of the nuclear spin bath induced by complex many-body interaction effects. We unambiguosly demonstrate that such a view on decoherence is greatly oversimplified; the relaxation of a spin qubit state is determined by three rather than two basic stages. The additional stage corresponds to the effect of coherent dephasing processes that occur in the nuclear spin bath that manifests itself by a relatively fast but incomplete non-monotonous relaxation of the central spin polarization at intermediate timescales. This observation changes our understanding of the electron spin qubit decoherence mechanisms in solid state systems.

Spin coupling damp decay of force cantilever microscopy design based on Grover's algorithm magnetic resonance quantum computing

We displayed the nuclear spin coupling and dipole polarisation in magnetic resonance microscopy based on quantum calculation. When radio frequency (rf) probing operated nuclear spins on the nanometer localisation, Grover’s quantum algorithm can be realised by polarisation enhanced states using pulse sequence and width according to the interaction between RF and spins. We theoretically proposed two-qubits quantum system of density matrix to achieve quantum Grover’s algorithm in spin damp and frequency shift based on magnetic resonance microscopy. The nuclear spins were operated by pulse time sequences of cyclic adiabatic inversion, and controlled the quantum spin magnetic moment state to achieve the superposition. The resonance spins excited by radio frequency coil and magnetic tip were measured by the nuclear magnetic moment, spectrum and density matrix. The results indicated that the density matrix was used to read out quantum spectrum image. Grover’s algorithm can perform search faster than their classical counterparts. The force microscopy properties of spin damp decay holds great promise of magnetic resonance in quantum computing, quantum communication. Theoretically the algorithm is accelerated but not 100% in a rate of success.

Ion Conduction Mechanism of a Viral Proton Channel from Solid-State NMR

Mei Hong, Department of Chemistry, Iowa State University, Ames, IAThe M2 protein of the influenza virus forms a proton-selective channel that is important for the lifecycle of the virus. Using high-resolution magic-angle-spinning (MAS) solid-state NMR spectroscopy, we have obtained rich information on the proton-conduction mechanism in this prototypical ion channel. The proton-selective residue, a histidine in the transmembrane (TM) domain of M2, undergoes microsecond reorientations, at the same time exchanging protons with water molecules. The rate and energy barrier of the reorientation motion and the kinetics of proton exchange are quantified through measurements of 15N exchange NMR spectra, motionally averaged nuclear-spin couplings, and 1H chemical shifts. The pH-dependent charged state and the rotameric structure of the histidine rings were determined from chemical shifts and internuclear distances. Aromatic interactions between the histidine and an adjacent tryptophan residue provide novel insight into the two-orders-of-magnitude difference between the histidine-water proton exchange rate and the actual proton flux into the virion. Comparison of the 15N spectra of wild-type M2 with a mutant with higher proton conductance revealed that histidine - water proton exchange not only involved transformation of the neutral imidazole to the cationic imidazolium, but also involved transitions between the two neutral tautomeric states of histidine, indicating that quantum-mechanical tunneling is a second mechanism for proton relay. Mechanistic insights obtained from the TM domain of M2 are extended to influenza B virus M2 and to a longer construct of the protein to investigate the influence the extra-membrane domains on proton conduction.Acknowledgements: NIH grant GM088204.