Hyperfine Research Articles

Electric Field Dependence of EPR Hyperfine Coupling Constants.

In this article, we introduce a simple but reliable method to calculate the electric field dependence of the isotropic hyperfine coupling tensor Aiso for free radicals. This dependence, also referred to as the Bloembergen effect, can be of interest in analyzing EPR experiments for solid-state materials but is rarely studied for isolated radicals in the gaseous phase. The proposed method uses the numerical differentiation of the field-perturbed A tensor and, consequently, as a purely numerical method, does not depend on a quantum chemical method used to determine the hyperfine tensor A. To test the performance of the proposed method, we used a set of 28 systems, including seven organic radicals, the majority of which were taken from a recent benchmark study by Bartlett's group. We employed the well-tested and robust density functional theory (DFT) functional, namely CAM-B3LYP, and the variant of the CCSD method based on local pair natural orbitals, namely DLPNO-CCSD to calculate the Aiso tensor itself, and all first derivatives or Bloembergen effect constants ai(1).

Microwave spectrum and molecular structure calculations for η4-butadiene ruthenium tricarbonyl

The microwave spectrum of η4-butadiene ruthenium tricarbonyl was measured in the 5–15 GHz frequency range using a Flygare-Balle type pulsed beam Fourier transform microwave (FTMW) spectrometer. The rotational constants for the 102Ru isotopologue were determined to have the following values: A = 932.20099(42), B = 858.03248(47) and C = 831.35161(37) MHz. The centrifugal distortion constant dJ is 0.0862(29)kHz. 22 a-dipole and 4c-dipole transitions were measured. Extensive high-level G16 calculations were made using DFT and MP2 methods with various basis sets, some including core-potentials (ECP). The best structure was calculated with Gaussian 16 using B3LYP/def2-QZVPP, which includes a core potential (ECP). Extensive all-electron calculations were made based on the best ECP structure to predict 101Ru and 99Ru quadrupole coupling strengths. Quadrupole hyperfine structure splittings were measured for both 101Ru and 99Ru. The hyperfine structure splittings for the 101Ru nuclear quadrupole were measured, yielding the values of 1.5χaa = 98.12(17) MHz and 0.25(χbb-χcc) = 36.059(30). Measured hyperfine structure splittings for 99Ru quadrupole coupling yielded the values of 1.5χaa = 16.99(77) MHz and 0.25(χbb-χcc) = 6.23(32). These values are in reasonable agreement with some of the all-electron calculations.

Cr–Sc co-substituted nickel-cobalt nanospinel ferrites: An investigation of their structural, magnetic properties and hyperfine interactions

The chromium and scandium co-substituted nickel-cobalt nanospinel ferrites (NSFs) having general formula of Co0.5Ni0.5ScxCrxFe2-2xO4 (CoNiScCr) (x ≤ 0.10) have been fabricated through the sol-gel route and citric acid as fuel and characterized by X-ray diffractometry (XRD), 57Fe Mössbauer spectroscopy, vibrating sample magnetometry (VSM), and finally by scanning and transmission electron microscopy techniques (SEM and TEM, respectively). The crystallite size (Dmax) values of the products were estimated to lay between 31 and 46 nm, which was calculated by the Scherrer formula. It was observed that the doping ions’ concentration did not have a linear impact on the expansion of the lattice constant. SEM and TEM present the cubic shape of CoNiScCr NSFs. All ratios demonstrate highly agglomerated cubic particles with diverse sizes. Both XRD and EDX (Energy Dispersive X-ray Spectroscopy) analyses confirmed the absence of any impurity/phases. Through an analysis of hysteresis loops at 300 (RT = room temperature) and 20 K, along with a probe of temperature-induced alteration in magnetization M, the magnetic properties of CoNiScCr (x ≤ 0.10) NSFs have been thoroughly investigated. Notably, all products exhibited complementary soft and hard magnetic behaviors at RT and 20 K, respectively. At 20 K, the observation of squareness ratio values surpassing 0.5 exhibits a single-domain behavior at this specific temperature. Magnetic parameters, in general, exhibit fluctuations with increasing doping content. Across the entire range of materials studied, a notable trend emerges as the temperature decreases, the magnetization in the zero field cooling curves shows a non-linear decrease, eventually stabilizing in the field cooling branches. The findings suggest that the inclusion of Sc3+/Cr3+ dopants can be utilized to manipulate and achieve desired magnetic properties in Co–Ni ferrites. The spectra of Mössbauer analysis, which was utilized to establish the distribution of cations, presented four magnetic sextets for all samples. Doped ions are substituted with Fe3+ ions at the B site.

Measurement of transition frequencies and hyperfine constants of molecular iodine at 520.2 nm

We measured the transition frequencies of the hyperfine components in the four lines (P(34) 39-0, R(36) 39-0, P(33) 39-0, and R(35) 39-0) of the B-X transitions of molecular iodine at 520.2 nm. The 520.2 nm laser was generated by wavelength-converting the output of a 1560.6 nm external-cavity diode laser using a dual-pitch periodically poled lithium niobate (PPLN) waveguide. The frequencies were measured by counting the heterodyne beats between the laser stabilized at the frequencies of the hyperfine components and a frequency comb synchronized with a hydrogen maser. We determined the transition frequencies of the a1 components with relative uncertainties of 1×10−11; the uncertainty was limited by the impurity of the molecular iodine in the cell. From the measured hyperfine splitting frequencies, we calculated the hyperfine constants of these four transitions to obtain the rotational dependence of the excited-state hyperfine constants.

Combined microwave and optical spectroscopy for hyperfine structure analysis in thulium atoms

Combined microwave and optical spectroscopy for hyperfine structure analysis in thulium atoms

Bidentate Substrate Binding Mode in Oxalate Decarboxylase.

Oxalate decarboxylase is an Mn- and O2-dependent enzyme in the bicupin superfamily that catalyzes the redox-neutral disproportionation of the oxalate monoanion to form carbon dioxide and formate. Its best-studied isozyme is from Bacillus subtilis where it is stress-induced under low pH conditions. Current mechanistic schemes assume a monodentate binding mode of the substrate to the N-terminal active site Mn ion to make space for a presumed O2 molecule, despite the fact that oxalate generally prefers to bind bidentate to Mn. We report on X-band 13C-electron nuclear double resonance (ENDOR) experiments on 13C-labeled oxalate bound to the active-site Mn(II) in wild-type oxalate decarboxylase at high pH, the catalytically impaired W96F mutant enzyme at low pH, and Mn(II) in aqueous solution. The ENDOR spectra of these samples are practically identical, which shows that the substrate binds bidentate (κO, κO') to the active site Mn(II) ion. Domain-based local pair natural orbital coupled cluster singles and doubles (DLPNO-CCSD) calculations of the expected 13C hyperfine coupling constants for bidentate bound oxalate predict ENDOR spectra in good agreement with the experiment, supporting bidentate bound substrate. Geometry optimization of a substrate-bound minimal active site model by density functional theory shows two possible substrate coordination geometries, bidentate and monodentate. The bidentate structure is energetically preferred by ~4.7 kcal/mol. Our results revise a long-standing hypothesis regarding substrate binding in the enzyme and suggest that dioxygen does not bind to the active site Mn ion after substrate binds. The results are in agreement with our recent mechanistic hypothesis of substrate activation via a long-range electron transfer process involving the C-terminal Mn ion.

Osmium(III) Acetylacetonate and Its Missing Polymorph: A Magnetic and Structural Investigation.

Despite the potential for their application, the magnetic behavior of complexes containing 4d and 5d metal ions is underexplored, evidencing the need for benchmark multi-technique studies on simple molecules. We report here a structural and magnetic study on osmium(III) acetylacetonate [Os(acac)3]. X-ray single crystal diffraction did not allow us to determine the structure of the β-polymorph of [Os(acac)3]. The combined magnetic (dc magnetic measurements on powder and cantilever torque magnetometry on single crystal) and spectroscopic (electron paramagnetic resonance, EPR) characterization is here used to provide further evidence that its structure is indeed the one of the orthorhombic "missing polymorph", analogous to the ruthenium(III) derivative. Our study shows that all acetylacetonate complexes of the eighth group of the periodic table show dimorphism and are isomorphic. The EPR characterization allowed the experimental assessment of the easy axis nature of the ground doublet and the determination of the first hyperfine coupling in an osmium complex. Torque magnetometry, applied here for the first time on an osmium-based molecule, determined the orientation of the easy axis along the pseudo C3 axis of the complex. Ac magnetometric measurements revealed in-field slow relaxation of the magnetization further slowed by the suppression of dipolar fields via magnetic dilution in the isostructural gallium(III) analogue.

Optimization of polarization spectroscopy signal for laser-frequency stabilization

Abstract We experimentally generate polarization spectroscopy (error) signals corresponding to the D2-line hyperfine transitions, F g = 2 → F e = 1 , 2 , 3 of 87Rb, and F g = 3 → F e = 2 , 3 , 4 of 85Rb, and show that the strongest error signals correspond to the closed hyperfine transitions (oscillator strength ∼ 0.7 ), F g = 2 → F e = 3 and F g = 3 → F e = 4 , respectively. We make the generated error signal robust to fluctuations in external parameters by finding optimum values for the vapor cell temperature and pump-probe intensities at two different beam diameters. We further employ these optimized error signals to directly (without the need for frequency/phase modulation) lock the laser frequency—reducing the rms drift/linewidth from ∼ 10 MHz to < 500 kHz, when measured over a ∼ 60 min duration. In addition, by comparing theoretically calculated and experimentally measured error signals for the pump intensities ranging from ∼ 0.1 I sat 0 − 10 I sat 0 (where, I sat 0 ∼ 1.6 mW cm−2 is the two-level saturation intensity for the Rb D2-line transitions), we discuss the applicability and limitations of existing numerical and analytical approaches based on a full multi-level rate equation model for polarization spectroscopy.

Spin Dynamics of Radical Pairs Using the Stochastic Schrödinger Equation in MolSpin.

The chemical reactivity of radical pairs is strongly influenced by the interactions of electronic and nuclear spins. A detailed understanding of these effects requires a quantum description of the spin dynamics that considers spin-dependent reaction rates, interactions with external magnetic fields, spin-spin interactions, and the loss of spin coherence caused by coupling to a fluctuating environment. Modeling real chemical and biochemical systems, which frequently involve radicals with multinuclear spin systems, poses a severe computational challenge. Here, we implement a method based on the stochastic Schrödinger equation in the software package MolSpin. Large electron-nuclear spin systems can be simulated efficiently, with asymmetric spin-selective recombination reactions, anisotropic hyperfine interactions, and nonzero exchange and dipolar couplings. Spin-relaxation can be modeled using the stochastic time-dependence of spin interactions determined by molecular dynamics and quantum chemical calculations or by allowing rate coefficients to be explicitly time-dependent. The flexibility afforded by this approach opens new avenues for exploring the effects of complex molecular motions on the spin dynamics of chemical transformations.

Effective light-induced Hamiltonian for atoms with large nuclear spin

Ultracold fermionic atoms, having two valence electrons, exhibit a distinctive internal state structure, wherein the nuclear spin becomes decoupled from the electronic degrees of freedom in the ground electronic state. Consequently, the nuclear spin states are well isolated from the environment, rendering these atomic systems an opportune platform for quantum computation and quantum simulations. Coupling with off-resonance light is an essential tool to selectively and coherently manipulate the nuclear spin states. In this paper, we present a systematic derivation of the effective Hamiltonian for the nuclear spin states of ultracold fermionic atoms due to such an off-resonance light. We obtain compact expressions for the scalar, vector, and tensor light shifts taking into account both linear and quadratic contributions to the hyperfine splitting. The analysis has been carried out using the Green operator approach and solving the corresponding Dyson equation. Finally, we analyze different scenarios of light configurations which lead to the vector- and tensor-light shifts, as well as the pure spin-orbit coupling for the nuclear spin. Published by the American Physical Society 2024

Constraints on the variation of physical constants, equivalence principle violation, and a fifth force from atomic experiments

The aim of this paper is to derive limits on various forms of “new physics” using atomic experimental data. Interactions with dark energy and dark matter fields can lead to space-time variations of fundamental constants, which can be detected through atomic spectroscopy. In this study, we examine the effects of a varying nuclear mass mN and nuclear radius rN on two transition ratios: the comparison of the two-photon transition in atomic hydrogen with the hyperfine transition in Cs133 based clocks, and the ratio of optical clock frequencies in Al+ and Hg+. The sensitivity of these frequency ratios to changes in mN and rN enables us to derive new limits on the variations of the proton mass, quark mass, and the QCD parameter θ. Additionally, we consider the scalar field generated by the Yukawa-type interaction of feebly interacting hypothetical scalar particles with Standard Model particles in the presence of massive bodies such as the Sun and Moon. Using the data from the Al+/Hg+, Yb+/Cs, and Yb+(E2)/Yb+(E3) transition frequency ratios, we place constraints on the interaction of the scalar field with photons, nucleons, and electrons for a range of scalar particle masses. We also investigate limits on the Einstein equivalence principle (EEP) violating term (c00) in the Standard Model extension (SME) Lagrangian and the dependence of fundamental constants on gravity. Published by the American Physical Society 2024

A comparison of pulse and CW EPR [formula omitted]-relaxation measurements of an inhomogeneously broadened nitroxide spin probe undergoing Heisenberg spin exchange 2. The intercept discrepancy

Experimental confirmation of a theoretical prediction of a non-linear broadening of the spin packets of nitroxide free radicals due to Heisenberg spin exchange at low concentrations, C, is presented. A recent demonstration that spectra with resolved proton hyperfine structure may be analyzed efficiently and accurately was utilized to confirm the theory. As C→0, a plot of the spin-packet line width (SPW) curves downward due to the presence of proton hyperfine couplings that increase the number of distinguishable quantum spin states. At higher C, the broadening is linear with C and the results for the spin exchange rate constant determined from the slope of the broadening of the average spin-packet line width and electron spin echo measurements are in agreement. It is shown that applying modest digital smoothing does not change the values of the SPW. An example of a practical application of these methods to published work is presented, allowing an enigma to be resolved.

Structure determination of 2,5-difluorophenol by microwave spectroscopy

The Fourier transform microwave spectrum of 2,5-difluorophenol has been obtained in the centimeter wave range, revealing only one conformer stabilized by an intramolecular interaction where the hydrogen atom of the OH group is in a syn orientation to the fluorine atom at the 2-ring position. The heavy atom backbone structure was obtained from the rotational constants of the 13C and 18O isotopologues whose spectra were measured in natural abundance. The spectrum of the OD isotopologue obtained by deuterium enrichment was also measured, and the nuclear quadrupole hyperfine structures arising from deuterium were analyzed. The semi-experimental equilibrium structure (reSE) was determined by correcting the experimental rotational constants with the vibration-rotation interaction constants obtained via an anharmonic force field. Quantum chemical calculations at various levels of theory were used to support results from the experiments.

McFine: python-based Monte-Carlo multi-component hyperfine structure fitting

Abstract Modelling complex line emission in the interstellar medium (ISM) is a degenerate, high-dimensional problem. Here, we present McFine, a tool for automated multi-component fitting of emission lines with complex hyperfine structure, in a fully automated way. We use Markov chain Monte Carlo (MCMC) to efficiently explore the complex parameter space, allowing for characterising model denegeracies. This tool allows for both local thermodynamic equilibrium (LTE) and radiative-transfer (RT) models. McFine can fit individual spectra and data cubes, and for cubes encourage spatial coherence between neighbouring pixels. It is also built to fit the minimum number of distinct components, to avoid overfitting. We have carried out tests on synthetic spectra, where in around 90 per cent of cases it fits the correct number of components, otherwise slightly fewer components. Typically, Tex is overestimated and τ underestimated, but accurate within the estimated uncertainties. The velocity and line widths are recovered with extremely high accuracy, however. We verify McFine by applying to a large Atacama Large Millimeter/submillimeter Array (ALMA) N2H+ mosaic of an high-mass star forming region, G316.75-00.00. We find a similar quality of fit to our synthetic tests, aside from in the active regions forming O-stars, where the assumptions of Gaussian line profiles or LTE may break down. To show the general applicability of this code, we fit CO(J = 2-1) observations of NGC 3627, a nearby star-forming galaxy, again obtaining excellent fit quality. McFine provides a fully automated way to analyse rich datasets from interferometric observations, is open source, and pip-installable.

Atomistic Compositional Details and Their Importance for Spin Qubits in Isotope-Purified Silicon Quantum Wells.

Understanding crystal characteristics down to the atomistic level increasingly emerges as a crucial insight for creating solid state platforms for qubits with reproducible and homogeneous properties. Here, isotope concentration depth profiles in a SiGe/28Si/SiGe heterostructure are analyzed with atom probe tomography (APT) and time-of-flight secondary-ion mass spectrometry down to their respective limits of isotope concentrations and depth resolution. Spin-echo dephasing times and valley energy splittings EVS around have been observed for single spin qubits in this quantum well (QW) heterostructure, pointing toward the suppression of qubit decoherence through hyperfine interaction with crystal host nuclear spins or via scattering between valley states. The concentration of nuclear spin-carrying 29Si is 50 ± 20ppm in the 28Si QW. The resolution limits of APT allow to uncover that both the SiGe/28Si and the 28Si/SiGe interfaces of the QW are shaped by epitaxial growth front segregation signatures on a few monolayer scale. A subsequent thermal treatment, representative of the thermal budget experienced by the heterostructure during qubit device processing, broadens the top SiGe/28Si QW interface by about two monolayers, while the width of the bottom 28Si/SiGe interface remains unchanged. Using a tight-binding model including SiGe alloy disorder, these experimental results suggest that the combination of the slightly thermally broadened top interface and of a minimal Ge concentration of % in the QW, resulting from segregation, is instrumental for the observed large . Minimal Ge additions <1%, which get more likely in thin QWs, will hence support high EVS without compromising coherence times. At the same time, taking thermal treatments during device processing as well as the occurrence of crystal growth characteristics into account seems important for the design of reproducible qubitproperties.

CPT and Lorentz symmetry tests with hydrogen using a novel in-beam hyperfine spectroscopy method applicable to antihydrogen experiments

We present a Rabi-type measurement of two ground-state hydrogen hyperfine transitions performed in two opposite external magnetic field directions. This puts first constraints at the level of ▪ on a set of coefficients of the Standard Model Extension, which were not measured by previous experiments. Moreover, we introduce a novel method, applicable to antihydrogen hyperfine spectroscopy in a beam, that determines the zero-field hyperfine transition frequency from the two transitions measured at the same magnetic field. Our value, ▪, is in agreement with literature at a relative precision of 0.44 ppb. This is the highest precision achieved on hydrogen in a beam, improving over previous results by a factor of 6.

Impurity Ions Mn&lt;sup&gt;2+&lt;/sup&gt; and Fe&lt;sup&gt;3+&lt;/sup&gt; as Paired Spin Labels for the Study of Structural Transformations in Phyllosilicates by the ESR Method

Impurity paramagnetic ions Mn2+ and high spin Fe3+ (S = 5/2) are shown to be very informative “paired spin labels” to investigate structural transformations in natural aluminosilicate clay minerals by ESR spectroscopy. Second derivative ESR (SD ESR) enables to detect minor narrow lines of the ions against the background of intense broad lines of other paramagnetic impurities. Complex SD ESR spectra of the ions are explained by the Jahn-Teller effect and hyperfine interactions with OH-groups. SD ESR spectra before and after heating (620°C and 900°C) proved transformations of octahedral crystal cells accompanied by the loss of the OH-groups, displacement of the ions to equivalent positions.

Redox Transformations of the OX063 Radical in Biological Media: Oxidative Decay of Initial Trityl with Further Formation of Structurally-Modified TAM.

Being a low-toxic and hydrophilic representative of TAM, OX063 has shown its suitability for in-vivo and in-cell EPR experiments and design of spin labels. Using 13C labeling, we investigated the course of oxidative degradation of OX063 into quinone-methide (QM) under the influence of superoxide as well as further thiol-promoted reduction of QM into TAM radical, which formally corresponds to substitution of a carboxyl function by a hydroxyl group. We found these transformations being quantitative in model reactions mimicking specific features of biological media and confirmed the presence of these reactions in the blood and liver homogenate of mice in vitro. The emergence of the trityl with the hydroxyl group can be masked by an initial TAM in EPR spectra and may introduce distortions into EPR-derived oximetry data if they have been obtained for objects under hypoxia. 13C labeling allows one to detect its presence, considering its different hyperfine splitting constant on 13C1 (2.04 mT) as compared to OX063 (2.30 mT). The potential involvement of these reactions should be considered when using TAM in spin-labeling of biopolymers intended for subsequent EPR experiments, as well as in the successful application of TAM in experiments in vivo and in cell.

The Effect of Spin Relaxation on Magnetic Compass Sensitivity in ErCry4a.

This study explores the impact of thermal motion on the magnetic compass mechanism in migratory birds, focusing on the radical pair mechanism within cryptochrome photoreceptors. The coherence of radical pairs, crucial for magnetic field inference, is curbed by spin relaxation induced by intra-protein motion. Molecular dynamics simulations, density-functional-theory-based calculations, and spin dynamics calculations were employed, utilizing Bloch-Redfield-Wangsness (BRW) relaxation theory, to investigate compass sensitivity. Previous research hypothesized that European robin's cryptochrome 4a (ErCry4a) optimized intra-protein motion to minimize spin relaxation, enhancing magnetic sensing compared to the plant Arabidopsis thaliana's cryptochrome 1 (AtCry1). Different correlation times of the nuclear hyperfine coupling constants in AtCry1 and ErCry4a were indeed found, leading to distinct radical pair recombination yields in the two species, with ErCry4a showing optimized sensitivity. However, this optimization is likely negligible in realistic spin systems with numerous nuclear spins. Beyond insights in magnetic sensing, the study presents a detailed method employing molecular dynamics simulations to assess for spin relaxation effects on chemical reactions with realistically modelled protein motion, relevant for studying radical pair reactions at finite temperature.

AC Zeeman effect in microfabricated surface traps.

Quantum processors and atomic clocks based on trapped ions often utilize an ion's hyperfine transition as the qubit state or frequency reference, respectively. These states are a good choice because they are insensitive in first order to magnetic field fluctuations, leading to long coherence times and stable frequency splittings. In trapped ions, however, these states are still subject to the second order AC Zeeman effect due to the necessary presence of an oscillating magnetic field used to confine the ions in a Paul trap configuration. Here, we measure the frequency shift of the 2S1/2 hyperfine transition of a 171Yb+ ion caused by the radio frequency (RF) electromagnetic field used to create confinement in several microfabricated surface trap designs. By comparing different trap designs, we show that two key design modifications significantly reduce the AC Zeeman effect experienced by the ion: (1) an RF ground layer routed directly below the entire RF electrode, and (2) a symmetric RF electrode. Both of these changes lead to better cancellation of the AC magnetic field and, thus, overall reduced frequency shifts due to the AC Zeeman effect and reduced variation across the device. These improvements enable a more homogeneous environment for quantum computing and can reduce errors for precision applications such as atomic clocks.