Hyperfine Research Articles

Saturated absorption spectroscopy of 87Rb atoms using structured light: Observation of narrow hyperfine and crossover resonances

Abstract An experiment on the saturated absorption spectroscopy (SAS) of 87Rb-D2 line is performed using the Laguerre-Gaussian (LG) beam as structured light. The theoretical simulation of which is done by considering a four-level atom-laser coupled system. The theoretically simulated spectra fairly match with the experimentally observed spectra. The line-width narrowing behavior of both the observed hyperfine and crossover resonances in the Doppler-broadened probe absorption spectra is attributed by the spatially dependent Rabi frequency of the pump LG beam irrespective of the characteristics of the probe beam. The results also illustrated that the narrowing behavior of the line shapes of the hyperfine structure using the LG beam is universal in nature, i.e. irrespective of hyperfine or crossover transitions. This structured light-induced narrowing of line-width of the sub Doppler hyperfine and crossover resonances can be utilized for high-precision laser frequency locking at a particular hyperfine or crossover transition. Moreover, a significant narrowing of hyperfine and crossover resonances with the variation of the orbital angular momentum (OAM) number of the LG beam shows that the generated SAS signal can be manipulated by using the OAM of the structured light as a control knob.

Mixing effects on spectroscopy and partonic observables of heavy mesons with logarithmic confining potential in a light-front quark model

Using the variational principle, we systematically investigate the mass spectra and wave functions of both 1S and 2S state heavy pseudoscalar (P) and vector (V) mesons within the light-front quark model. This approach incorporates a Coulomb plus logarithmic confinement potential to accurately describe the constituent quark and antiquark dynamics. Additionally, spin hyperfine interactions are introduced perturbatively to compute the masses of pseudoscalar and vector mesons. The present analyses of the 1S and 2S states require the consideration of mixing between them to account for empirical constraints. These constraints include the mass gap ΔMP>ΔMV, where ΔMP(V)=MP(V)2S−MP(V)1S and the hierarchy of the decay constants f1S>f2S. We find the optimal value of the mixing angle to be θ=18°, significantly enhancing the consistency between our spectroscopic predictions and the experimental data compiled by the Particle Data Group. Furthermore, based on the predicted mass, the newly observed resonance BJ(5840) could be assigned as a 21S0 state in the B meson family. The study also reports various pertinent observables, including twist-two distribution amplitudes, electromagnetic form factors, charge radii, ξ moments, and transition form factors that are found to be consistent with both available lattice simulations and experimental data. In addition, our predicted branching ratios for the channels of B+→τ+ντ as well as rare decays of B0 and Bs0 appear in accordance with experimental data. Published by the American Physical Society 2024

A theoretical study on muoniated N-heterocyclic carbenes using path integral molecular dynamics

Several N-heterocyclic carbenes (NHCs) are experimentally observed upon the addition of muonium (Mu), and the hyperfine coupling constants (HFCCs) of muon are measured. Theoretical investigation of Mu has been challenging due to significant quantum effects. Herein, we performed an ab initio path integral molecular dynamics (PIMD) simulation, which accurately considers multi-dimensional quantum effects, to theoretically investigate muoniated 1,3-dihydro-2H-imidazole-2-ylidene (Mu-IY). Our findings indicate that quantum effects have two contradictory contributions: the quantum effect of bond vibrations increases the HFCC values, whereas that of out-of-plane angular vibrations decreases the HFCC values. Moreover, we show that the HFCC values of other NHCs can be predicted without the PIMD simulations by applying the structural changes caused by the quantum effect derived from the PIMD simulations of Mu-IY.

The contribution of methyl groups to electron spin decoherence of nitroxides in glassy matrices.

Long electron spin coherence lifetimes are crucial for high sensitivity and resolution in many pulse electron paramagnetic resonance (EPR) experiments aimed at measuring hyperfine and dipolar couplings, as well as in potential quantum sensing applications of molecular spin qubits. In immobilized systems, methyl groups contribute significantly to electron spin decoherence as a result of methyl torsional quantum tunneling. We examine the electron spin decoherence dynamics of the nitroxide radical 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) in both a methyl-free solvent and a methyl-containing solvent at cryogenic temperature. We model nitroxide and solvent methyl effects on decoherence using cluster correlation expansion (CCE) simulations extended to include methyl tunneling and compare the calculations to experimental data. We show that by using the methyl tunneling frequency as a fit parameter, experimental Hahn echo decays can be reproduced fairly well, allowing structural properties to be investigated in silico. In addition, we examine the Hahn echo of a hypothetical system with an unpaired electron and a single methyl to determine the effect of geometric configuration on methyl-driven electron spin decoherence. The simulations show that a methyl group contributes the most to electron spin decoherence if it is located between 2.5 and 6-7Å from the electron spin, with its orientation being of secondary importance.

Constraining P and T violating forces with chiral molecules

New sources of parity and time-reversal violation are predicted by well motivated extensions of the Standard Model and can be effectively probed by precision spectroscopy of atoms and molecules. Chiral molecules have distinguished enantiomers which are related by parity transformation. Thus they are promising candidates to search for parity violation at molecular scales, which has yet to be observed. In this work, we show that precision spectroscopy of the hyperfine structure of chiral molecules is sensitive to new physics sources of parity and time-reversal violation. In particular, such a study can be sensitive to regions unexplored by terrestrial experiments of a new chiral spin-1 particle that couples to nucleons. We explore the potential to hunt for time-reversal violation in chiral molecules and show that it can be a complementary measurement to other probes. We assess the feasibility of such hyperfine metrology and project the sensitivity in CHDBrI+. Published by the American Physical Society 2024

New spin structure constraints on hyperfine splitting and proton Zemach radius

The 1S hyperfine splitting in hydrogen is measured to an impressive ppt precision and will soon be measured to ppm precision in muonic hydrogen. The latter measurement will rely on theoretical predictions, which are limited by knowledge of the proton polarizability effect Δpol. Data-driven evaluations of Δpol have long been in significant tension with baryon chiral perturbation theory. Here we present improved results for Δpol driven by new spin structure data, reducing the long-standing tension between theory and experiment and halving the dominating uncertainty in hyperfine splitting calculations.

High‐Frequency Electron Paramagnetic Resonance and Electron‐Nuclear Double Resonance Spectroscopy Study of the Ga Vacancy in β‐Ga2O3

The Ga vacancy (VGa) defect in β‐Ga2O3, generated by proton irradiation, is studied using high‐frequency electron paramagnetic resonance (EPR) and electron‐nuclear double resonance spectroscopy. The previous X‐band EPR studies of this defect, attributed to VGa2−, are extended to higher frequencies (240 GHz) and lower temperatures (T = 6 K). The spin Hamiltonian parameters of the VGa2− center are determined: electron spin S = 1/2, g‐tensor: gb = 2.0313, gc = 2.0079, and ga = 2.0025; the hyperfine interaction parameters with 2 equivalent Ga neighbors: Ab = 14.0 G, Ac = 14.6 G, and Aa* = 12.8 G for 69Ga; the superhyperfine interaction with distant Ga neighbors ASHF(69Ga) = 11 MHz; and the quadrupole interaction Qb(69Ga) = 0.32 MHz and Qb(71Ga) = 0.22 MHz. These results shall allow to refine the assignment of this center to a split vacancy or an unrelaxed VGa2− defect.

Ka-Band Rotational Spectroscopy of Succinimide and N-Chlorosuccinimide.

Succinimide and its derivatives are cyclic five-membered rings that appear in a variety of natural products and are widely used in organic synthesis. From a structural standpoint, succinimide contains an NH group in the ring which interacts with two adjacent carbonyl groups, pushing the ring structure toward planarity at the expense of increasing ring strain and eclipsing interactions among the out-of-plane hydrogen atoms in the two CH2 groups. Previous quantum chemical calculations at different levels of theory have predicted both a nonplanar C2 structure and a planar C2v structure, the latter of which is the most consistent with gas-phase electron diffraction measurements. Here, we report the pure rotational spectra of succinimide and N-chlorosuccinimide in the 26.5-40.0 GHz range using chirped-pulse Fourier transform microwave spectroscopy, supported by coupled cluster and density functional theory quantum chemical calculations. The spectra were fit to Watson's A-reduced effective Hamiltonian, including both 35Cl and 37Cl isotopologues of N-chlorosuccinimide as well as the N and Cl quadrupole hyperfine interactions. On the basis of the agreement with quantum chemical calculations and the measured inertial defects, we find that the rotational spectra are consistent with a planar ring structure, with a maximum out-of-plane angle of ≤5°.

Utilizing the multifrequency resonances of the electron spins in diamond nitrogen-vacancy centers under strong radio frequency driving for quantum sensing

Multifrequency resonances in the pulsed-optically detected magnetic resonance (ODMR) spectra of electron spins in ensemble nitrogen-vacancy (NV) centers in diamonds are investigated under strong radio frequency (RF) driving at a MHz frequency range and weak microwave driving at a GHz frequency range in a bias static magnetic field for quantum sensing applications. First, we demonstrate that the coherent destruction of tunneling, which leads to the disappearance of the main resonance peaks, can be utilized for precise calibration of the RF amplitude. Next, we clarify the condition for enhancing the sensitivity of a DC magnetic field under strong RF driving at the RF frequency that matches the split frequency due to the hyperfine interaction between 15N nuclear spins and the NV electron spins. Our findings indicate that strong RF driving increases the sensitivity of the DC magnetic field by enhancing the ODMR contrast and reducing the linewidth. The above results contribute to certifying the quantitative accuracy of RF imaging and enhancing the sensitivity of the DC magnetic field imaging using ensemble NV centers in diamonds.

Singular Points of the Radiation Spectrum of Leaky Surface Magnon Polarons

Within the dissipation-free approach, for a magnetic layer separating two semi-bounded ideal fluids, it is shown that, at the point of the phonon radiation spectrum where leaky surface magnon polarons of the “dark” state are formed (of interference or symmetry-protected type) at the interface with an acoustically less dense medium, both the numerator and the denominator of the input wave impedance can independently become zero (at the very point of existence of a bound state in the continuum, they vanish simultaneously). The calculation was performed for a two-sublattice model of an antiferromagnet, which simultaneously takes into account magnetoelastic, inhomogeneous exchange, and hyperfine coupling. Conditions have been found under which the mechanisms of formation of bound states in the spectrum of phonon radiation of leaky magnon polarons involving quasi-electronic or quasi-nuclear magnons are fundamentally different: elastodynamic or elastostatic.

Keep Your TEMPO Up: Nitroxide Radicals as Sensors of Intermolecular Interactions

This study examines experimental data on the influence of the surrounding medium and non-covalent interactions on the isotropic hyperfine coupling constant, Aiso(14N), of the stable nitroxide radical 2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO) in solution. The data were used to identify a density functional theory functional/basis set combination that accurately reproduces the experimental Aiso(14N) values. The variations in Aiso(14N) due to external factors are two orders of magnitude greater than the accuracy of its experimental measurements, making Aiso(14N) a highly sensitive experimental probe for quantifying these effects. Additionally, it was found that the proton-accepting ability of the N-O• moiety in TEMPO resembles that of the P=O moiety, enabling the simultaneous formation of two equally strong hydrogen bonds.

Tuning the Electronic And Transport Properties of CaMoO4 Nanofibers with High-Spin Ni for Efficient and Stable Supercapacitors.

Calcium molybdate (CaMoO4) has recently garnered considerable attention for supercapacitors due to its stable crystal structure and cost-effective preparation. However, CaMoO4 prepared by traditional processes still suffered from insufficient electrochemical active sites and poor electrical conductivity so far, thus leading to the performance of CaMoO4-based supercapacitors being inferior to the state-of-the-art ones. CaMoO4 nanofibers with a high specific surface area exhibit great potential for supercapacitors due to their ability to offer increased charge storage. Herein, mesoporous CaMoO4 nanofibers anchored with Ni nanoparticles were fabricated via electrospinning combined with subsequent thermal treatment. Density functional theory calculation and UV-vis spectrophotometer results show that high-spin state Ni nanoparticles can tune the electronic structure of CaMoO4 nanofibers, decreasing the band gap by about 0.67 eV. Electron paramagnetic resonance (EPR) studies imply that Ni doping influences the electronic structure by reducing the oxygen vacancy concentration and introducing hyperfine structures associated with Ni spins. These can result in higher power and energy density in supercapacitors. As a result, a specific capacitance of 1253.7 F·g-1 at a current density of 0.5 A·g-1 and an 86% retention rate after 2000 cycles at a higher current density of 5 A·g-1 have been achieved for Ni0.25Ca0.75MoO4-based supercapacitor. Furthermore, an asymmetric supercapacitor (ASC) device with the optimized CaMoO4/Ni//AC structure has been demonstrated with the energy density of 49.43 Wh·kg-1 and power density of 2700 W·kg-1, thus enabling lightening a red light-emitting diode. The current strategy might pave the way for CaMoO4 for practical applications for high-power supercapacitors.

DFT and EPR Study of Spin Excitations in Oxidized Thiophene-Based Conjugated Oligomers

Comparison of data obtained using the density functional theory (DFT) and electron paramagnetic resonance (EPR) method made it possible to establish the composition and state of spin charge carries in the poly(3, 4-ethylenedioxythiophene) (PEDOT) and poly(3-alkylthiophene) (P3AT) oligomers. The coexistence of several polarons on the P3AT chain, the properties of which are governed by the structure of the substituents, is identified. All terms of the spin Hamiltonians of different oligomers were obtained, and their high-resolution EPR spectra were calculated. The structure of the P3AT substituents is shown to influence the polaron spin state and hyperfine interaction with its own microenvironment. The prospects of the approaches used in the work to develop electronic and spintronic elements with spin-controlled parameters are shown.

Rydberg atom-based microwave electrometry using polarization spectroscopy

Abstract In this study, we investigated Rydberg atom-based microwave electrometry using polarization spectroscopy in a room-temperature vapor cell. By measuring Autler-Townes splitting in the electromagnetically induced transparency (EIT) spectrum, we determined that the minimum measurable microwave electric field is approximately five times lower than conventional EIT techniques. The results are well reproduced by a full optical Bloch equation model, which takes into account all the hyperfine levels involved. Subsequently, the EIT setup was used to characterize a custom microwave cylindrical lens, which increases the field at the focus by a factor of three, decreasing the minimum measurable microwave electric field by the same amount. Our results indicate that the combination of polarization spectroscopy and a microwave lens may enhance microwave electrometry, and may allow its use as a secondary standard.

Longitudinal and Transverse 1H Nuclear Magnetic Resonance Relaxivities of Lanthanide Ions in Aqueous Solution up to 1.4 GHz/33 T.

The longitudinal and transverse nuclear magnetic resonance relaxivity dispersion (NMRD) of 1H in water induced by the paramagnetic relaxation enhancement (PRE) of dissolved lanthanide ions (Ln3+) can become very strong. Longitudinal and transverse 1H NMRD for Gd3+, Dy3+, Er3+ and Ho3+ were measured from 20 MHz/0.47 T to 1382 MHz/32.5 T, which extended previous studies by a factor of more than two in the frequency range. For the NMRD above 800 MHz, we used a resistive magnet, which exhibits reduced field homogeneity and stability in comparison to superconducting and permanent NMR magnets. These drawbacks were addressed by dedicated NMRD methods. In a comparison of NMRD measurements between 800 MHz and 950 MHz performed in both superconducting and resistive magnets, it was found that the longitudinal relaxivities were almost identical. However, the magnetic field fluctuations of the resistive magnet strongly perturbed the transverse relaxation. The longitudinal NMRDs are consistent with previous work up to 600 MHz. The transverse NMRD nearly scales with the longitudinal one with a factor close to one. The data can be interpreted within a PRE model that comprises the dipolar hyperfine interactions between the 1H and the paramagnetic ions, as well as a Curie spin contribution that is dominant at high magnetic fields for Dy3+, Er3+ and Ho3+. Our findings provide a solid methodological basis and valuable quantitative insights for future high-frequency NMRD studies, enhancing the measurement accuracy and applicability of PRE models for paramagnetic ions in aqueous solutions.

Engineering Rydberg-pair interactions in divalent atoms with hyperfine-split ionization thresholds

Quantum information processing with neutral atoms relies on Rydberg excitation for entanglement generation. While the use of heavy divalent or open-shell elements, such as strontium or ytterbium, has benefits due to their optically active core and a variety of possible qubit encodings, their Rydberg structure is generally complex. For some isotopes in particular, hyperfine interactions are relevant even for highly excited electronic states. We employ multichannel quantum defect theory to infer the Rydberg structure of isotopes with nonzero nuclear spin and perform nonperturbative Rydberg-pair interaction calculations. We find that due to the high level density and sensitivities to external fields, experimental parameters must be precisely controlled. Specifically in Sr87, we study an intrinsic Förster resonance, unique to divalent atoms with hyperfine-split thresholds, which simultaneously provides line stability with respect to external field fluctuations and enhanced long-range interactions. Additionally, we provide parameters for pair states that can be effectively described by single-channel Rydberg series. The explored pair states provide exciting opportunities for applications in the blockade regime, as well as for more exotic long-range interactions such as largely flat, distance-independent potentials. Published by the American Physical Society 2024

Observation of dynamic nuclear polarization echoes.

It is demonstrated that the time evolution of the electron-nuclear polarization transfer process during pulsed dynamic nuclear polarization (DNP) can be reversed on a microsecond timescale, leading to the observation of DNP echoes. The DNP echoes are induced by consecutive application of two pulse trains that produce effective Hamiltonians that differ only in the sign of the effective hyperfine coupling. The experiments have been performed on a frozen solution of trityl radicals in water/glycerol on a homebuilt X-band electron paramagnetic resonance/DNP spectrometer at 80 kelvins. We envisage that DNP echoes will play an important role in future development of pulsed DNP for sensitivity-enhanced nuclear magnetic resonance, hyperfine spectroscopy, and quantum sensing.

Fabrication of Nd-Ho Cosubstituted Co0.5Ni0.5Fe2O4 Nanospinel Ferrites and Exploration of Their Microstructure, Magnetic, and Electromagnetic Characteristics.

The composition and hyperfine structures of Nd3+-Ho3+ ions cosubstituted CoNi nanospinel ferrites (Co0.5Ni0.5NdxHoxFe2-2xO4 (x ≤ 0.05) NSFs) as well as their magnetic and electrodynamic behavior have been presented. The compound Nd-Ho → CoNiFe2O4 (x ≤ 0.05) NSFs were produced using the sol-gel method. XRD powder patterns indicated phase- and substituent-induced modifications of crystallites. The SEM analysis indicated the homogeneous distribution of grains with Nd-Ho cosubstitution. It was found that the values of x had an impact on the hyperfine magnetic field of the A and B sites. The cation distribution was determined by using Mössbauer spectroscopy. The M-H loops' investigations showed that the current NSFs behave ferrimagnetically at both room and low temperatures. An almost continuous rise in the strength of the coercive field was noticed with a rise in Ho-Nd content. The value of calculated squareness ratio values was above 0.5 at both temperatures, entailing that the studied NSFs' structure is made of single magnetic domains. The electromagnetic characteristics of the samples can be explained by the main contribution to electromagnetic absorption being the electric energy losses. Electromagnetic absorbed materials can be applied to provide electromagnetic compatibility and develop functional electromagnetic shields.

Enhancing Photogenerated Radical Pair Properties in Donor-Chromophore-Acceptor Systems for Quantum Information Applications.

We report on new donor-chromophore-acceptor triads BDX-ANI-NDI and BDX-ANI-xy-NDI where the BDX donor is 2,2,6,6-tetramethylbenzo[1,2-d;4,5-d]bis[1,3]dioxole, the ANI chromophore is 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, the NDI acceptor is naphthalene-1,8:4,5-bis(dicarboximide), and xy is a 2,5-xylyl spacer. The results on these compounds are compared to the analogous derivatives having a p-methoxyaniline (MeOAn) as the donor. BDX•+ has no nitrogen atoms and only a single hydrogen atom coupled to its unpaired electron spin, and therefore has significantly decreased hyperfine interactions compared to MeOAn•+. We use femtosecond transient absorption (fsTA) and nanosecond TA (nsTA) spectroscopies, the latter with an applied static magnetic field, to study the charge transfer dynamics and determine the spin-spin exchange interaction (J) for BDX•+-ANI-NDI•- and BDX•+-ANI-xy-NDI•- at both ambient and cryogenic temperatures. Time-resolved electron paramagnetic resonance (EPR) and pulse-EPR measurements on these spin-correlated radical pairs (SCRPs) were used to probe their spin dynamics. We demonstrate that BDX•+-ANI-xy-NDI•- has an unusually long lifetime of ∼550 μs in glassy butyronitrile (PrCN) at 85 K, which makes it useful for pulse-EPR studies that target quantum information science (QIS) applications. We also show that rotation of the BDX group about the single bond linking it to the neighboring phenyl group has a significant impact on the spin dynamics, and in particular the magnitude of J. By comparing the results on these compounds to the analogous MeOAn series, insights into design principles for creating improved spin-correlated radical pair systems for QIS studies are obtained.

Toward Quantum Noses: Quantum Chemosensing Based on Molecular Qubits in Metal-Organic Frameworks.

ConspectusQuantum sensing leverages quantum properties to enhance the sensitivity and resolution of sensors beyond their classical sensing limits. Quantum sensors, such as diamond defect centers, have been developed to detect various physical properties, including magnetic fields and temperature. However, the spins of defects are buried within dense solids, making it difficult for them to strongly interact with molecular analytes. Therefore, nanoporous materials have been implemented in combination with electron spin center of molecules (molecular qubits) to produce quantum chemosensors that can distinguish various chemical substances. Molecular qubits have a uniform structure, and their properties can be precisely controlled by changing their chemical structure. Metal-organic frameworks (MOFs) are suitable for supporting molecular qubits because of their high porosity, structural regularity, and designability. Molecular qubits can be inserted in the MOF structures or adsorbed as guest molecules. The qubits in the MOF can interact with analytes upon exposure, providing an effective and tunable sensing platform.In this Account, we review the recent progress in qubit-MOF hybrids toward the realization of room-temperature quantum chemosensing. Molecular qubits can be introduced in controlled concentrations at targeted positions by exploiting metal ions, ligands, or guests that compose the MOF. Heavy metal-free organic chromophores have several outstanding features as molecular qubits; namely, they can be initialized by light irradiation and exhibit relatively long coherence times of submicroseconds to microseconds, even at room temperature. One detection method involves monitoring the hyperfine interaction between the electron spins of the molecular qubits and the nuclear spins of the analyte incorporated in the pore. There is also an indirect detection method that relies on the motional change in molecular qubits. If the motion of the molecular qubit changes with the adsorption of the analyte, it can be detected as a change in the spin relaxation process. This mechanism is unique to qubits exposed in nanopores, not observed in conventional qubits embedded in dense solids.By maximizing the guest recognition ability of MOFs and the environmental sensitivity of qubits, quantum chemosensing that recognizes specific chemical species in a highly selective and sensitive manner may be possible. It is difficult to distinguish between diverse chemical species by employing only one combination of MOF and qubit, but by creating arrays of different qubit-MOF hybrids, it would become possible to distinguish between various analytes based on pattern recognition. Inspired by the human olfactory mechanism, we propose the use of multiple qubit-MOF hybrids and pattern recognition to identify specific molecules. This system represents a quantum version of olfaction, and thus we propose the concept of a "quantum nose." Quantum noses may be used to recognize biometabolites and biomarkers and enable new medical diagnostic technologies and olfactory digitization.