Nuclear Spin Research Articles

Probing the 13C nuclear spin relaxation of diamond nanoparticles with solid-state NMR

Probing the 13C nuclear spin relaxation of diamond nanoparticles with solid-state NMR

Accurate hyperfine tensors for solid state quantum applications: case of the NV center in diamond

The decoherence of point defect qubits is often governed by the electron spin-nuclear spin hyperfine interaction that can be parameterized by using ab inito calculations in principle. So far most of the theoretical works have focused on the hyperfine interaction of the closest nuclear spins, while the accuracy of the predictions for distinct nuclear spins is barely discussed. Here we demonstrate for the case of the NV center in diamond that the absolute relative error of the computed hyperfine parameters can exceed 100% using an industry standards first-principles code. To overcome this issue, we implement an alternative method and report on significantly improved hyperfine values with O\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{{{{\\mathcal{O}}}}}}}}$$\\end{document}(1%) relative mean error at all distances. The provided accurate hyperfine data for the NV center enables high-precision simulation of NV quantum nodes for quantum information processing and positioning of nuclear spins by comparing experimental and theoretical hyperfine data.

Tunable Quantum Coherence of Luminescent Molecular Spins Organized via Block Copolymer Self‐Assembly

AbstractElectronic or nuclear spins represent promising candidates of qubits for applications in quantum information technologies and spintronic devices. However, it remains a challenge to achieve scalable and spatially defined organization of a large number of spins as qubits, which is essential in the feasible fabrication of quantum circuits. We report a strategy of block copolymer self‐assembly to organize molecular spins as qubits across molecular to micro‐/nano‐scales in polymeric films of organic luminescent radicals centered in star‐like block copolymers. We have achieved not only scalable and spatially defined organization of the molecular spins in polymeric films with long‐range periodic ordering but also controllable spin‐lattice relaxation dynamics and spin coherence lifetimes that can be finely tuned by the domain sizes and rigidities of the polymeric matrices.

Quantifying the effects of peripheral substituents on the spin-lattice relaxation of a vanadyl molecular quantum bit

Electron spin superpositions represent a critical component of emergent quantum technologies in computation, sensing, encryption, and communication. However, spin relaxation (T1) and decoherence (Tm) represent major obstacles to the implementation of molecular quantum bits (qubits). Synthetic strategies have made substantial progress in enhancing spin coherence times by minimizing contributions from surrounding electron and nuclear spins. For room-temperature operation, however, the lifetime of spin coherence becomes limited by coupling with vibrational modes of the lattice. Using pulse electron paramagnetic resonance (EPR) spectroscopy, we measure the spin-lattice relaxation of a vanadyl tetrapyrazinoporphyrazine complex appended with eight peripheral 2,6-diisopropylphenol groups (VOPyzPz-DIPP) and compare it to the relaxation of the archetypical vanadyl phthalocyanine molecular qubit (VOPc). The added peripheral groups lead to distinctly different spin relaxation behavior. While similar relaxation times are observed at low temperatures and ambient conditions, significant changes are observed for the orientation dependence of T1 at 100 K, as well as the temperature dependence of T1 over the intermediate temperature range spanning [Formula: see text]10–150 K. These results can be tentatively interpreted as arising from loosened spin-phonon coupling selection rules and a greater number of accessible acoustic and optical modes contributing to the spin relaxation behavior of VOPyzPz-DIPP relative to VOPc.

Anisotropic relaxation of nuclear spins dipolar energy of water molecules in two-dimensional nanopores - A single crystal NMR study

Energy transfer from Zeeman to dipolar order discovered by Jeener et al. is usually observed in solids with a strong dipole-dipole interaction of nuclear spins. It is not observed in liquids, where fast molecular motion completely averages this interaction. The intermediate case, when the dipole-dipole interaction of nuclear spins is only partially averaged, has been poorly studied. We report on the first measurement of an angular-dependent proton spin relaxation of a dipolar reservoir in mobile water molecules confined in the interlayer pores of a vermiculite single crystal. In this layered crystal, the intramolecular dipole-dipole interactions of nuclear spins are only partially averaged due to the restricted anisotropic molecular motion in nanopores. We show that this allows the formation of dipolar echo. We measured the spin-lattice relaxation times of the dipolar order T1D at different angles between the normal to the crystal surface and the applied magnetic field and obtained a distinct angular dependence of T1D. The minimum relaxation rate R1D was found around the magic angle of 54.74°.

Zero to ultralow magnetic field NMR of [1−13C]pyruvate and [2−13C]pyruvate enabled by SQUID sensors and hyperpolarization

Accurately characterizing magnetic resonance of molecules at zero to ultralow magnetic field (nTs-µTs) is challenging, due to vanishingly small sensitivity, which depends on the thermal equilibrium polarization of the nuclear spins and instrumentation. We overcome the former limitation with the parahydrogen-based hyperpolarization method SABRE-SHEATH (signal amplification by reversible exchange in shield enables alignment transfer to heteronuclei). This method allows for the continuous transfer of spin order from parahydrogen to a substrate via chemical exchange, reaching polarization levels of some percent (level equivalent to C13 polarization at 20 kT). We address the latter with our application of a superconducting quantum interference device (SQUID)-based detector setup that allows for broadband detection (dc-MHz) with exquisite sensitivity over its entire range. Here, we present the results of our comprehensive characterization of [1−13C]pyruvate and [2−13C]pyruvate, hyperpolarized via SABRE-SHEATH, from zero field to 100 µT. To this end, we show low-noise, high-resolution spectra for both molecules, detecting how the NMR spectrum changes from the -coupling dominated zero-field spectrum to the strongly coupled spectrum, and then finally to the conventional high-field, otherwise known Zeeman-dominated spectrum. We also analytically derive the evolution of product operators in arbitrary magnetic fields, which aid in the understanding of the differences between spin evolution and spin-coupling regimes. We predict and confirm that the absence of spin precession at zero field can result in observable oscillation of magnetization along one axis with a frequency of the -coupling constant, no observable spin evolution, or observing spin evolution that corresponds to “forbidden” transitions at high field. The zero-field spectra with their near-dc signals reveal different relaxation rates for the different spin states of hyperpolarized C13 pyruvates, demonstrating the utility of SQUID detectors and hyperpolarization for the characterization of magnetic resonance phenomena. Published by the American Physical Society 2024

Microscopic understanding of NMR signals by dynamic mean-field theory for spins

A recently developed dynamic mean-field theory for disordered spins (spinDMFT) is shown to capture the spin dynamics of nuclear spins very well. The key quantities are the spin autocorrelations. In order to compute the free induction decay (FID), pair correlations are needed in addition. They can be computed on spin clusters of moderate size which are coupled to the dynamic mean fields determined in a first step by spinDMFT. We dub this versatile approach non-local spinDMFT (nl-spinDMFT). It is a particular asset of nl-spinDMFT that one knows from where the contributions to the FID stem. We illustrate the strengths of nl-spinDMFT in comparison to experimental data for CaF2. Furthermore, spinDMFT provides the dynamic mean fields explaining the FID of the nuclear spins of 13C in adamantane up to some static noise. The spin Hahn echo in adamantane is free from effects of static noise and agrees excellently with the spinDMFT results without further fitting.

Ligand Effects on the Spin Relaxation Dynamics and Coherent Manipulation of Organometallic La(II) Potential Qudits.

We present pulsed electron paramagnetic resonance (EPR) studies on three La(II) complexes, [K(2.2.2-cryptand)][La(Cp')3] (1), [K(2.2.2-cryptand)][La(Cp″)3] (2), and [K(2.2.2-cryptand)][La(Cptt)3] (3), which feature cyclopentadienyl derivatives as ligands [Cp' = C5H4SiMe3; Cp″ = C5H3(SiMe3)2; Cptt = C5H3(CMe3)2] and display a C3 symmetry. Long spin-lattice relaxation (T1) and phase memory (Tm) times are observed for all three compounds, but with significant variation in T1 among 1-3, with 3 being the slowest relaxing due to higher s-character of the SOMO. The dephasing times can be extended by more than an order of magnitude via dynamical decoupling experiments using a Carr-Purcell-Meiboom-Gill (CPMG) sequence, reaching 161 μs (5 K) for 3. Coherent spin manipulation is performed by the observation of Rabi quantum oscillations up to 80 K in this nuclear spin-rich environment (1H, 13C, and 29Si). The high nuclear spin of 139La (I = 7/2), and the ability to coherently manipulate all eight hyperfine transitions, makes these molecules promising candidates for application as qudits (multilevel quantum systems featuring d quantum states; d >2) for performing quantum operations within a single molecule. Application of HYSCORE techniques allows us to quantify the electron spin density at ligand nuclei and interrogate the role of functional groups to the electron spin relaxation properties.

Realization of robust quantum noise characterization in the presence of coherent errors

Complex quantum systems and their various applications are susceptible to noise of coherent and incoherent nature. Characterization of noise and its sources is an open, key challenge in quantum technology applications, especially in terms of distinguishing between inherent incoherent noise and systematic coherent errors. In this paper, we study a scheme of repeated sequential measurements that enables the characterization of incoherent errors by reducing the effects of coherent errors. We demonstrate this approach using a coherently controlled nitrogen vacancy in diamond, coupled to both a natural nuclear spin bath (non-Markovian) and to experimentally controlled relaxation through an optical pumping process (nearly Markovian). Our results show mitigation of coherent errors both for Markovian and non-Markovian incoherent noise profiles. We apply this scheme to the estimation of the dephasing time (T2*) due to incoherent noise. We observe an improved robustness against coherent errors in the estimation of dephasing time (T2*) compared to the standard (Ramsey) measurement.

Morphology, physical, and structural aspects of copper nanoparticles induced- metal phosphate nanocompounds for gamma ray shielding and magnetic sensing applications

The inorganic nanocompounds were synthesized by solid state reaction with the composition 10Li2O+(30-x)Sb2O3 + xZnO + 59.5P2O5 + 0.5Cu (in mol%). SEM morphographs of the samples confirmed the grain size ≈0.5–2.5 μm. The EDAX spectra of the samples confirmed presence of copper (Cu) nanoparticles (<2 wt%) in the composition. The EDAX studies showed energy dispersion of Kα- photons by reactivity of elements P, Cu, and Zn, while the element Sb has shown dispersion of Lα- photons up to 10 keV. Mass attenuation coefficient (MAC) has exhibited a few discontinuities (bumps) at low energies (<10 keV) due to K, L- absorption edges of various elements (such as P, Cu, Zn, and Sb) presented in the samples. The shrinking of Phosphorous-Phosphorous separation (dP-P) from 4.716 Ao to 3.990 Ao indicated the greater solidity (or density) of the prepared nanocompounds at higher content of ZnO. XRD spectra showed the presence of major crystallites such as LiPO3, Li3PO4, Li6P6018, SbPO4, Cu3PO4, Cu2P2O7, Cu3[PO4]2, Zn[PO3]2, Zn2P2O7, ZnP4O11, and LiZnPO4 in the prepared nanocompounds. The average crystallite size was determined in the range of 35–83 nm. FTIR spectra of these compounds displayed the [PO2]−, [PO3]−, [PO4]3−, and [ZnO4] units along with linkages P─O─P, O─P─O, Sb─O─Sb, Cu─O─Cu, etc. A band due to vibrations of Cu─O bond has been observed in the range of 466–478 cm−1, which endorses the contribution of copper nanoparticles in the solid state reaction of the metal phosphate nanocompounds. A partially resolved hyperfine structure of magnetic resonance signals corresponding to g|| ≈2.4 and g⊥ ≈2.05 were observed due to the presence of an anisotropic hyperfine interaction of the electron spin (S = 1/2) with the nuclear spin (I = 3/2) of copper isotopes (63Cu and 65Cu) in the samples.

Single-step parity check gate set for quantum error correction

A key requirement for an effective quantum error correction (QEC) scheme is that the physical qubits have error rates below a certain threshold. The value of this threshold depends on the details of the specific QEC scheme, and its hardware-level implementation. This is especially important with parity-check circuits, which are the fundamental building blocks of QEC codes. The standard way of constructing the parity check circuit is using a universal set of gates, namely sequential CNOT gates, single-qubit rotations and measurements. We exploit the insight that a QEC code does not require universal logic gates, but can be simplified to perform the sole task of error detection and correction. By building gates that are fundamental to QEC, we can boost the threshold and ease the experimental demands on the physical hardware. We present a rigorous formalism for constructing and verifying the error behavior of these gates, linking the physical measurement of a process matrix to the abstract error models commonly used in QEC analysis. This allows experimentalists to directly map the gates used in their systems to thresholds derived for a broad-class of QEC codes. We give an example of these new constructions using the model system of two nuclear spins, coupled to an electron spin, showing the potential benefits of redesigning fundamental gate sets using QEC primitives, rather than traditional gate sets reliant on simple single and two-qubit gates.

Biological and equilibrium studies of Co(II), Cu(II), Zn(II), and Cd(II) complexes of 1‐formyl‐3‐semicarbazide: Docking studies

1‐Formyl‐3‐semicarbazide (FSC, HL) and its metal complexes with Co(II), Cu(II), Zn(II), and Cd(II) ions have been synthesized and characterized by elemental analysis, liquid chromatography‐mass spectrometry (LC–MS), infrared (IR), electronic, nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopy, thermogravimetric analysis (TGA), magnetic susceptibility, and conductivity measurements. The chelates are non‐electrolytic in nature with distorted octahedral geometry. The kinetic and thermodynamic properties were calculated using the Coats–Redfern relation results in positive enthalpy change values and negative entropy change values. The equilibrium studies of FSC with Co(II), Zn(II), and Cd(II) ion have been carried out by potentiometric pH titrations in 70% v/v DMF‐water medium at 303 K and 0.1 M (KNO3) ionic strength. The study revealed that FSC is monobasic acid with pKa value of 8.84. The stability constants suggested the formation of 1:1 Co(II)‐FSC complex, and Zn(II)‐FSC and Cd(II)‐FSC systems revealed the formation of both 1:1 and 1:2 complexes in the solution. DNA binding studies for the metal chelates have been carried out using electronic absorption spectra, fluorescence emission spectra, and viscosity measurements revealing groove binding for Co(II), and Zn(II) complexes, and intercalation mode of binding for Cu(II)‐FSC complex with CT‐DNA. The Kb values from absorption studies are Co(II)‐FSC = 0.9990 × 102, Cu(II)‐FSC = 2.433 × 104, and Zn(II)‐FSC = 8.277 × 102 M−1, and the KSV values from the competitive fluorescence emission studies are Co(II)‐FSC = 0.19212 and Cu(II)‐FSC = 0.11482 M−1. Molecular docking carried out for both ligand and its Co(II) and Zn(II) complexes also revealed groove mode of binding, and Cu(II) complex showed intercalative mode of binding. The inhibition constants for HL, Co(II), Cu(II), and Zn(II) are 1460, 0.478, 0.122, and 0.194 μM, respectively. The antimicrobial activity has been studied using agar disk diffusion method against Escherichia coli and Bacillus subtilis. FSC has been found to be more active against gram +ve and gram –ve bacteria than its metal chelates.

Suppressing effect of shortening vapor cell stem on polarization-induced magnetic gradient relaxation of Xe in NMR co-magnetometers

The Rb polarization-induced magnetic field gradient is one of the crucial sources of Xe spin relaxation in NMR co-magnetometers. The additional volume of the atomic vapor cell stem can enhance the effective magnetic field gradient through the diffusion effect of the optically polarized-Rb atoms, which affects the spin relaxation properties of Xe and degrades the long-term stability of NMR co-magnetometers. Based on the discrete steps random walk diffusion model, the magnetic gradient relaxation properties of Xe diffusing in an asymmetric cell composed of a cubic part and a cylindrical tube (stem) are characterized. Simulation results indicate that a shorter stem can effectively prolong the nuclear spin relaxation time under a constant magnetic field gradient. To verify this conclusion, a cell stem truncating actuator is developed using a high-power CO2 laser to shorten the cell stem, and the magnetic field gradient coil is used to perform the gradient compensation to examine the impact of various stem lengths on the spin relaxation rate. Experiments indicate that under the influence of atomic diffusive motions, shortening the stem length can effectively suppress the polarization-induced magnetic gradient and increase the 129Xe transverse relaxation time from 4.5 s to 21 s. The study posts practical applications for vapor cells with a stem, which is expected to enhance the performance of atomic spin co-magnetometers.

Quantum interference in atom-exchange reactions.

Chemical reactions, where bonds break and form, are highly dynamic quantum processes. A fundamental question is whether coherence can be preserved in chemical reactions and then harnessed to generate entangled products. Here we investigated this question by studying the 2KRb → K2 + Rb2 reaction at 500 nK, focusing on the nuclear spin degrees of freedom. We prepared the initial nuclear spins in KRb in an entangled state by lowering the magnetic field to where the spin-spin interaction dominates and characterized the preserved coherence in nuclear spin wavefunction after the reaction. We observed an interference pattern that is consistent with full coherence at the end of the reaction, suggesting that entanglement prepared within the reactants could be redistributed through the atom-exchange process.

Nuclear spin relaxation mediated by donor-bound and free electrons in wide CdTe quantum wells

Nuclear spin relaxation mediated by donor-bound and free electrons in wide CdTe quantum wells

Coherent Microwave, Optical, and Mechanical Quantum Control of Spin Qubits in Diamond

AbstractDiamond has emerged as a highly promising platform for quantum network applications. Color centers in diamond fulfill the fundamental requirements for quantum nodes: they constitute optically accessible quantum systems with long‐lived spin qubits. Furthermore, they provide access to a quantum register of electronic and nuclear spin qubits and they mediate entanglement between spins and photons. All these operations require coherent control of the color center's spin state. This review provides a comprehensive overview of the state‐of‐the‐art, challenges, and prospects of such schemes, including high‐fidelity initialization, coherent manipulation, and readout of spin states. Established microwave and optical control techniques are reviewed, and moreover, emerging methods such as cavity‐mediated spin–photon interactions and mechanical control based on spin–phonon interactions are summarized. For different types of color centers, namely, nitrogen–vacancy and group‐IV color centers, distinct challenges persist that are subject of ongoing research. Beyond fundamental coherent spin qubit control techniques, advanced demonstrations in quantum network applications are outlined, for example, the integration of individual color centers for accessing (nuclear) multiqubit registers. Finally, the role of diamond spin qubits in the realization of future quantum information applications is described.

Entanglement of nanophotonic quantum memory nodes in a telecom network

A key challenge in realizing practical quantum networks for long-distance quantum communication involves robust entanglement between quantum memory nodes connected by fibre optical infrastructure1–3. Here we demonstrate a two-node quantum network composed of multi-qubit registers based on silicon-vacancy (SiV) centres in nanophotonic diamond cavities integrated with a telecommunication fibre network. Remote entanglement is generated by the cavity-enhanced interactions between the electron spin qubits of the SiVs and optical photons. Serial, heralded spin-photon entangling gate operations with time-bin qubits are used for robust entanglement of separated nodes. Long-lived nuclear spin qubits are used to provide second-long entanglement storage and integrated error detection. By integrating efficient bidirectional quantum frequency conversion of photonic communication qubits to telecommunication frequencies (1,350 nm), we demonstrate the entanglement of two nuclear spin memories through 40 km spools of low-loss fibre and a 35-km long fibre loop deployed in the Boston area urban environment, representing an enabling step towards practical quantum repeaters and large-scale quantum networks.

Magic Angle Spinning Solid-State 13C Photochemically Induced Dynamic Nuclear Polarization by a Synthetic Donor-Chromophore-Acceptor System at 9.4 T.

Solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) is a nuclear magnetic resonance spectroscopy technique in which nuclear spin hyperpolarization is generated upon optical irradiation of an appropriate donor-acceptor system. Until now, solid-state photo-CIDNP at high magnetic fields has been observed only in photosynthetic reaction centers and flavoproteins. In the present work, we show that the effect is not limited to such biomolecular samples, and solid-state 13C photo-CIDNP can be observed at 9.4 T under magic angle spinning using a frozen solution of a synthetic molecular system dissolved in an organic solvent. Signal enhancements for the source molecule larger than a factor of 2300 are obtained. In addition, we show that bulk 13C hyperpolarization of the solvent can be generated via spontaneous 13C-13C spin diffusion at natural abundance.

Sensing Coherent Nuclear Spin Dynamics with an Ensemble of Paramagnetic Nitrogen Spins

The unpolarized spin environment surrounding a central spin qubit is typically considered as an incoherent source of dephasing, however, precise characterization and control of the spin bath can yield a resource for storing and sensing with quantum states. In this work, we use nitrogen-vacancy (NV) centers in diamond to measure the coherence of optically dark paramagnetic nitrogen defects (P1 centers) and detect coherent interactions between the P1 centers and a local bath of 13C nuclear spins. The dipolar coupling between the P1 centers and 13C nuclear spins is identified by signature periodic collapses and revivals in the P1 spin coherence signal. We then demonstrate, using a range of dynamical decoupling protocols, that the probing NV centers and the P1 spins are coupled to independent ensembles of 13C nuclear spins. Our work illustrates how the optically dark P1 spins can be used to extract information from their local environment and offers new insight into the interactions within a many-body system. Published by the American Physical Society 2024

Restriction on molecular fluxionality by substitution: A case study for the 1,10-dicyanobullvalene.

We show herein that 1,10-dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10-dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born-Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long-time limit, isomerizations of the 14 isomers, each with Cs symmetry, approach the "14 Cs → C7v" thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C7v symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un-explored properties e.g. for the equilibration dynamics of C10H10.