Frequency Electron Paramagnetic Resonance Research Articles

Spectroscopic and Theoretical Investigation of High-Spin Square-Planar and Trigonal Fe(II) Complexes Supported by Fluorinated Alkoxides.

The electronic structures and spectroscopic behavior of three high-spin FeII complexes of fluorinated alkoxides were studied: square-planar {K(DME)2}2[Fe(pinF)2] (S) and quasi square-planar {K(C222)}2[Fe(pinF)2] (S') and trigonal-planar {K(18C6)}[Fe(OC4F9)3] (T) where pinF = perfluoropinacolate and OC4F9 = tris-perfluoro-t-butoxide. The zero-field splitting (ZFS) and hyperfine structure parameters of the S = 2 ground states were determined using field-dependent 57Fe Mössbauer and high-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopies. The spin Hamiltonian parameters were analyzed with crystal field theory and corroborated by density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) calculations. Whereas the ZFS tensor of S has a small rhombicity, E/D = 0.082, and a positive D = 15.17 cm-1, T exhibits a negative D = -9.16 cm-1 and a large rhombicity, E/D = 0.246. Computational investigation of the structural factors suggests that the ground-state electronic configuration and geometry of T's Fe site are determined by the interaction of [Fe(OC4F9)3]- with {K(18C6)}+. In contrast, two distinct countercations of S/S' have a negligible influence on their [Fe(pinF)2]2- moieties. Instead, the distortions in S' are likely induced by the chelate ring conformation change from δλ, observed for S, to the δδ conformation, determined for S'.

Optically Active Spin Defects in Few-Layer Thick Hexagonal Boron Nitride.

Optically active spin defects in hexagonal boron nitride (hBN) are promising quantum systems for the design of two-dimensional quantum sensing units offering optimal proximity to the sample being probed. In this Letter, we first demonstrate that the electron spin resonance frequencies of boron vacancy centers (V_{B}^{-}) can be detected optically in the limit of few-atomic-layer thick hBN flakes despite the nanoscale proximity of the crystal surface that often leads to a degradation of the stability of solid-state spin defects. We then analyze the variations of the electronic spin properties of V_{B}^{-} centers with the hBN thickness with a focus on (i)the zero-field splitting parameters, (ii)the optically induced spin polarization rate and (iii)the longitudinal spin relaxation time. This Letter provides important insights into the properties of V_{B}^{-} centers embedded in ultrathin hBN flakes, which are valuable for future developments of foil-based quantum sensing technologies.

MEPROS – Modular electron paramagnetic resonance operating software for multifunctional high-frequency EPR spectrometer

We present a software solution developed in LabVIEW for a home-built High–Frequency Electron Paramagnetic Resonance (HF-EPR) spectrometer. A modular approach was applied to control the spectrometer subsystems and simplify the adaptation to hardware changes during the development. The solution implements measuring procedures for conventional Continuous Wave EPR (CW-EPR), Frequency–Swept EPR (FS-EPR), and Two-Dimensional EPR (2D-EPR) mapping, which are relevant in different cases. The software’s automation capabilities were tested in several trial measurements to obtain CW-EPR spectra of Silicon Carbide doped by vanadium (SiC + V) at various temperatures and microwave frequencies, multi-frequency spectra via 2D-EPR mapping, and dense FS-EPR data of a lithium phthalocyanine crystal rotated in a magnetic field. Several prospective modifications of the software are discussed in the conclusion. A modular character allows the easy re-use of code portions in other experimental setups. The spectrometer and the software are currently deployed and utilized in a laboratory of EPR spectroscopy at Central European Institute of Technology (CEITEC) in Brno, and data obtained by it has been already used in a number of publications.

An Integrated Reconfigurable Spin Control System on 180 nm CMOS for Diamond NV Centers

Solid-state electron spins are key building blocks for emerging applications in quantum information science, including quantum computers, quantum communication links, and quantum sensors. These solid-state spins are mainly controlled using complex microwave pulse sequences, which are typically generated using benchtop electrical instruments. Integration of the required electronics will enable realization of a scalable low-power and compact optically addressable quantum system. Here, we report an integrated reconfigurable quantum control system, which is used to find electron-spin resonance (ESR) frequency and perform Rabi, Ramsey, and Hahn-echo measurements for a nitrogen-vacancy (NV) center spin qubit in diamond. The chip can be programmed to synthesize an RF signal tunable from 1.6 to 2.6 GHz, which is modulated with a sequence of up to 4098 reconfigurable pulses with a pulse width and pulse-to-pulse delay adjustable from 10 ns to 42 ms and 18 ns to 42 ms, respectively, at a resolution of 2.5 ns. The 180-nm CMOS chip is fabricated within a footprint of 3.02 mm <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{2}$</tex-math> </inline-formula> and has a power consumption of 80 mW.

Terahertz EPR spectroscopy using a 36-tesla high-homogeneity series-connected hybrid magnet

Electron Paramagnetic Resonance (EPR) is a powerful technique to study materials and biological samples on an atomic scale. High-field EPR in particular enables extracting very small g-anisotropies in organic radicals and half-filled 3d and 4f metal ions such as MnII (3d5) or GdIII (4f7), and resolving EPR signals from unpaired spins with very close g-values, both of which provide high-resolution details of the local atomic environment. Before the recent commissioning of the high-homogeneity Series Connected Hybrid magnet (SCH, superconducting + resistive) at the National High Magnetic Field Laboratory (NHMFL), the highest-field, high-resolution EPR spectrometer available was limited to 25 T using a purely resistive “Keck” magnet at the NHMFL. Herein, we report the first EPR experiments performed using the SCH magnet capable of reaching the field of 36 T, corresponding to an EPR frequency of 1 THz for g = 2. The magnet’s intrinsic homogeneity (25 ppm, that is 0.9 mT at 36 T over 1 cm diameter, 1 cm length cylinder) was previously established by NMR. We characterized the magnet’s temporal stability (5 ppm, which is 0.2 mT at 36 T over one-minute, the typical acquisition time) using 2,2-diphenyl-1-picrylhydrazyl (DPPH). This high resolution enables resolving the weak g-anisotropy of 1,3-bis(diphenylene)-2-phenylallyl (BDPA), Δg = 2.5 × 10–4 obtained from measurements at 932 GHz and 33 T. Subsequently, we recorded EPR spectra at multiple frequencies for two GdIII complexes with potential applications as spin labels. We demonstrated a significant reduction in line broadening in Gd[DTPA], attributed to second order zero field splitting, and a resolution enhancement of g-tensor anisotropy for Gd[sTPATCN]-SL.

A 220 GHz-1.1THz continuous frequency and polarization tunable quasi-optical electron paramagnetic resonance spectroscopic system.

Here, we describe a custom-designed quasi-optical system continuously operating in the frequency range 220GHz to 1.1THz with a temperature range of 5-300K and magnetic fields up to 9T capable of polarization rotation in both transmitter and receiver arms at any given frequency within the range through a unique double Martin-Puplett interferometry approach. The system employs focusing lenses to amplify the microwave power at the sample position and recollimate the beam to the transmission branch. The cryostat and split coil magnets are furnished with five optical access ports from all three major directions to the sample sitting on a two-axes rotatable sample holder capable of performing arbitrary rotations with respect to the field direction, enabling broad accessibility to experimental geometries. Initial results from test measurements on antiferromagnetic MnF2 single crystals are included to verify the operation of the system.

Dual-radical-based molecular anisotropy and synergy effect of semi-conductivity and valence tautomerization in a photoswitchable coordination polymer.

Organic radicals are widely used as linkers or ligands to synthesize molecular magnetic materials. However, studies regarding the molecular anisotropies of radical-based magnetic materials and their multifunctionalities are rare. Herein, a photoisomerizable diarylethene ligand was used to form {[CoIII(3,5-DTSQ·-)(3,5-DTCat2-)]2(6F-DAE-py2)}·3CH3CN·H2O (o-1·3CH3CN·H2O, 6F-DAE-py2=1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene), a valence-tautomeric (VT) coordination polymer. We directly observed dual radicals for a single crystal using high-field/-frequency (∼13.3 T and ∼360GHz) electron paramagnetic resonance (EPR) spectroscopy along the c-axis, which was further confirmed by angle-dependent Q-band EPR spectroscopy. Moreover, a conductive anomaly close to the VT transition temperature was observed only when probes were attached at the ab plane of the single crystal, indicative of synergy between valence tautomerism and conductivity. Structural anisotropy studies and density functional theory (DFT) calculations revealed that this synergy is due to electron transfer associated with valence tautomerism. This study presents the first example of dual-radical-based molecular anisotropy and charge-transfer-induced conductive anisotropy in a photoswitchable coordination polymer.

Symmetry of the Hyperfine and Quadrupole Interactions of Boron Vacancies in a Hexagonal Boron Nitride

The concept of optically addressable spin states of deep level defects in wide band gap materials is successfully applied for the development of quantum technologies. Recently discovered negatively charged boron vacancy defects (VB) in hexagonal boron nitride (hBN) potentially allow a transfer of this concept onto atomic thin layers due to the van der Waals nature of the defect host. Here, we experimentally explore all terms of the VB spin Hamiltonian reflecting interactions with the three nearest nitrogen atoms by means of conventional electron spin resonance and high frequency (94 GHz) electron-nuclear double resonance. We establish symmetry, anisotropy, and principal values of the corresponding hyperfine interaction (HFI) and nuclear quadrupole interaction (NQI). The HFI can be expressed in the axially symmetric form as Aperp = 45.5 MHz and Apar = 87 MHz, while the NQI is characterized by quadrupole coupling constant Cq = 1.96 MHz with slight rhombisity parameter n = (Pxx - Pyy)/Pzz = -0.070. Utilizing a conventional approach based on a linear combination of atomic orbitals and HFI values measured here, we reveal that almost all spin density (84 %) of the VB electron spin is localized on the three nearest nitrogen atoms. Our findings serve as valuable spectroscopic data and direct experimental demonstration of the VB spin localization in a single two dimensional BN layer.

Collisional electron paramagnetic resonance frequency shifts in Cs-Rb-Xe mixtures

We report a measurement of the ratio of dimensionless enhancement factors ${\ensuremath{\kappa}}_{0}$ for $\mathrm{Cs}\text{\ensuremath{-}}^{129}\mathrm{Xe}$ and $\mathrm{Rb}\text{\ensuremath{-}}^{129}\mathrm{Xe}$ in the temperature range 115--140 ${}^{\ensuremath{\circ}}\mathrm{C}$; both pairs are used in spin-exchange optical pumping (SEOP) to produce hyperpolarized $^{129}\mathrm{Xe}$. ${\ensuremath{\kappa}}_{0}$ characterizes the amplification of the $^{129}\mathrm{Xe}$ magnetization contribution to the alkali-metal electronic effective field, compared to the case of a uniform continuous medium in classical magnetostatics. The measurement was carried out in ``hybrid'' vapor cells containing both Rb and Cs metal in a prescribed ratio, producing approximately the same vapor density for both. Alternating measurements of the optically detected electron paramagnetic resonance (EPR) frequency shifts caused by the SEOP polarization and subsequent sudden destruction of the same quantity of $^{129}\mathrm{Xe}$ magnetization were made for $^{133}\mathrm{Cs}$ and either $^{87}\mathrm{Rb}$ or $^{85}\mathrm{Rb}$. An important source of systematic error caused by power fluctuations in the pump laser that produced variable light shifts in the EPR frequency was characterized and then mitigated by allowing sufficient warm-up time for the pump laser. We measured ${({\ensuremath{\kappa}}_{0})}_{\mathrm{CsXe}}/{({\ensuremath{\kappa}}_{0})}_{\mathrm{RbXe}}=1.215\ifmmode\pm\else\textpm\fi{}0.007$ with no apparent temperature dependence. Based on our previous measurement ${({\ensuremath{\kappa}}_{0})}_{\mathrm{RbXe}}=518\ifmmode\pm\else\textpm\fi{}8$, we determine ${({\ensuremath{\kappa}}_{0})}_{\mathrm{CsXe}}=629\ifmmode\pm\else\textpm\fi{}10$, which is more precise than, but consistent with, a previous measurement made by J. Fang et al. [Chin. Phys. B 23, 063401 (2014)].

Hyperfine Decoupling of ESR Spectra Using Wavelet Transform.

The objective of spectral analysis is to resolve and extract relevant features from experimental data in an optimal fashion. In continuous-wave (cw) electron spin resonance (ESR) spectroscopy, both values of a paramagnetic center and hyperfine splitting caused by its interaction with neighboring magnetic nuclei in a molecule provide important structural and electronic information. However, in the presence of - and/or -anisotropy and/or large number of resonance lines, spectral analysis becomes highly challenging. Either high-resolution experimental techniques are employed to resolve the spectra in those cases or a range of suitable ESR frequencies are used in combination with simulations to identify the corresponding and values. In this work, we present a wavelet transform technique in resolving both simulated and experimental cW-ESR spectra by separating the hyperfine and super-hyperfine components. We exploit the multiresolution property of wavelet transforms that allow the separation of distinct features of a spectrum based on simultaneous analysis of spectrum and its varying frequency. We retain the wavelet components that stored the hyperfine and/or super-hyperfine features, while eliminating the wavelet components representing the remaining spectrum. We tested the method on simulated cases of metal-ligand adducts at L-, S-, and X-band frequencies, and showed that extracted values, hyperfine and super-hyperfine coupling constants from simulated spectra, were in excellent agreement with the values of those parameters used in the simulations. For the experimental case of a copper(II) complex with distorted octahedral geometry, the method was able to extract and hyperfine coupling constant values, and revealed features that were buried in the overlapped spectra.

Mapping Pigments in a Painting with Low Frequency Electron Paramagnetic Resonance Spectroscopy

An electron paramagnetic resonance (EPR) mobile universal surface explorer (MOUSE) was recently introduced for noninvasively studying paramagnetic pigments in paintings. This study determined that the EPR MOUSE could map the spatial locations of four pigments in a simple impasto painting. Results from three spectral identification algorithms were examined to assess their ability to identify the pigments using an unsupervised approach. Resulting pigment maps are displayed as colorized images of the spatial distribution of the pigments. All three algorithms produced reasonable representations of the painting. The algorithms achieved excellent true positive, true negative, false positive, and false negative rates of ≥0.95, ≥0.98, ≤0.02, and ≤0.05, respectively, for the identification of the pigments. We conclude that the EPR MOUSE is suitable for accurately mapping the location of paramagnetic pigments in a painting.

In Vivo Dynamic Nuclear Polarization Magnetic Resonance Imaging for the Evaluation of Redox-Related Diseases and Theranostics.

Significance:In vivo molecular and metabolic imaging is an emerging field in biomedical research that aims to perform noninvasive detection of tissue metabolism in disease states and responses to therapeutic agents. The imbalance in tissue oxidation/reduction (Redox) states is related to the onset and progression of several diseases. Tissue redox metabolism provides biomarkers for early diagnosis and drug treatments. Thus, noninvasive imaging of redox metabolism could be a useful, novel diagnostic tool for diagnosis of redox-related disease and drug discovery. Recent Advances:In vivo dynamic nuclear polarization magnetic resonance imaging (DNP-MRI) is a technique that enables the imaging of free radicals in living animals. DNP enhances the MRI signal by irradiating the target tissue or solution with the free radical molecule's electron paramagnetic resonance frequency before executing pulse sequence of the MRI. In vivo DNP-MRI with redox-sensitive nitroxyl radicals as the DNP redox contrast agent enables the imaging of the redox metabolism on various diseases. Moreover, nitroxyl radicals show antioxidant effects that suppress oxidative stress. Critical Issues: To date, considerable progress has been documented preclinically in the development of animal imaging systems. Here, we review redox imaging of in vivo DNP-MRI with a focus on the recent progress of this system and its uses in patients with redox-related diseases. Future Directions: This technique could have broad applications in the study of other redox-related diseases, such as cancer, inflammation, and neurological disorders, and facilitate the evaluation of treatment response as a theranostic tool. Antioxid. Redox Signal. 36, 172-184.

Quantitative study of the response of a single NV defect in diamond to magnetic noise

The nitrogen-vacancy (NV) defect in diamond is an efficient quantum sensor of randomly fluctuating signals via relaxometry measurements. In particular, the longitudinal spin relaxation of the NV defect accelerates in the presence of magnetic noise with a spectral component at its electron spin resonance frequency. We look into this effect quantitatively by applying a calibrated and tunable magnetic noise on a single NV defect. We show that an increase of the longitudinal spin relaxation rate translates into a reduction of the photoluminescence (PL) signal emitted under continuous optical illumination, which can be explained using a simplified three-level model of the NV defect. This PL quenching mechanism offers a simple, all-optical method to detect magnetic noise sources at the nanoscale.

Exchange Coupling in a Linear Chain of Three Quantum-Dot Spin Qubits in Silicon.

Quantum gates between spin qubits can be implemented leveraging the natural Heisenberg exchange interaction between two electrons in contact with each other. This interaction is controllable by electrically tailoring the overlap between electronic wave functions in quantum dot systems, as long as they occupy neighboring dots. An alternative route is the exploration of superexchange-the coupling between remote spins mediated by a third idle electron that bridges the distance between quantum dots. We experimentally demonstrate direct exchange coupling and provide evidence for second neighbor mediated superexchange in a linear array of three single-electron spin qubits in silicon, inferred from the electron spin resonance frequency spectra. We confirm theoretically, through atomistic modeling, that the device geometry only allows for sizable direct exchange coupling for neighboring dots, while next-nearest neighbor coupling cannot stem from the vanishingly small tail of the electronic wave function of the remote dots, and is only possible if mediated.

Dynamic Nuclear Polarization with Vanadium(IV) Metal Centers

Summary Dynamic nuclear polarization (DNP) harnesses the large polarization of electron spins to dramatically increase nuclear magnetic resonance (NMR) sensitivity. This study expands the scope of DNP beyond its traditional focus on hyperpolarizing the solvent network using exogenous polarizing agents (PAs). We introduce 1H DNP with endogenous V4+ centers positioned in a set of vanadyl complexes with tunable V4+-1H distances. We traced the polarization transfer from V4+ to 1H spins, specifically differentiating between direct V4+-1Hs polarization transfer and the 1H spin-diffusion-mediated bulk solvent 1H polarization buildup and illuminated the effect of the V4+-1H distance on these processes. These results deepen our understanding of polarization pathways and expand the catalog of PAs to broad-line transition metals. This study establishes crucial first steps toward employing strategically positioned endogenous paramagnetic metal centers for DNP and the conceptual framework of hyperfine DNP spectroscopy that merges both spatial and chemical diagnosis of target nuclear spins.

Going Low in a World Going High: The Physiologic Use of Lower Frequency Electron Paramagnetic Resonance.

Yakov Sergeevich Lebedev was a pioneer in high frequency EPR, taking advantage of the separation of g-factor anisotropy effects from nuclear hyperfine splitting and the higher frequency molecular motion sensitivity from higher frequency measurements8. This article celebrates a second EPR subfield in which Prof. Lebedev pioneered, EPR imaging. 9 We celebrate the clinical enhancements that are suggested in this low frequency work and imaging application to animal physiology at lower-than-standard EPR frequencies.

Demonstration of NV-detected ESR spectroscopy at 115 GHz and 4.2 T

High frequency electron spin resonance (ESR) spectroscopy is an invaluable tool for identification and characterization of spin systems. Nanoscale ESR using the nitrogen-vacancy (NV) center has been demonstrated down to the level of a single spin. However, NV-detected ESR has exclusively been studied at low magnetic fields, where the spectral overlap prevents clear identification of spectral features. In this work, we demonstrate NV-detected ESR measurements of single-substitutional nitrogen impurities in diamond at a NV Larmor frequency of 115 GHz and the corresponding magnetic field of 4.2 T. The NV-ESR measurements utilize a double electron-electron resonance sequence and are performed using both ensemble and single NV spin systems. In the single NV experiment, chirp pulses are used to improve the population transfer and for NV-ESR measurements. This work provides the basis for NV-based ESR measurements of external spins at high magnetic fields.

Nanoscale Detection of Magnon Excitations with Variable Wavevectors Through a Quantum Spin Sensor.

We report the optical detection of magnons with a broad range of wavevectors in magnetic insulator Y3Fe5O12 thin films by proximate nitrogen-vacancy (NV) single-spin sensors. Through multimagnon scattering processes, the excited magnons generate fluctuating magnetic fields at the NV electron spin resonance frequencies, which accelerate the relaxation of NV spins. By measuring the variation of the emitted spin-dependent photoluminescence of the NV centers, magnons with variable wavevectors up to ∼5 × 107 m-1 can be optically accessed, providing an alternative perspective to reveal the underlying spin behaviors in magnetic systems. Our results highlight the significant opportunities offered by NV single-spin quantum sensors in exploring nanoscale spin dynamics of emergent spintronic materials.

Adjustable coupling and in situ variable frequency electron paramagnetic resonance probe with loop-gap resonators for spectroscopy up to X-band.

In standard electron paramagnetic resonance (EPR) spectroscopy, the frequency of an experiment is set and the spectrum is acquired using the magnetic field as the independent variable. There are cases in which it is desirable instead to fix the field and tune the frequency such as when studying avoided level crossings. We have designed and tested an adjustable frequency and variable coupling EPR probe with loop-gap resonators (LGRs) that works at a temperature as low as 1.8 K. The frequency is tuned by adjusting the height of a dielectric piece of sapphire inserted into the gap of an LGR; coupling of the microwave antenna is varied with the height of the antenna above the LGR. Both coupling antenna and dielectric are located within the cryogenic sample chamber, but their motion is controlled with external micrometers located outside the cryostat. The frequency of the LGR (∼4 GHz) can be adjusted by more than 1 GHz (>25%). To cover a wide range of frequencies, different LGRs can be designed to cover frequencies up to X-band. We demonstrate the operation of our probe by mapping out avoided crossings for the Ni4 molecular nanomagnet to determine the tunnel splittings with high precision.

Pulse EPR of Triarylmethyl Probes: A New Approach for the Investigation of Molecular Motions in Soft Matter.

Triarylmethyl (TAM) radicals have become widely used free radicals in the past few years. Their electron spins have long relaxation times and narrow electron paramagnetic resonance (EPR) lines, which make them an important class of probes and tags in biological applications and materials science. In this work, we propose a new approach to characterize librations by means of TAM radicals. The temperature dependence of motional parameter ⟨α2⟩τc, where ⟨α2⟩ is the mean-squared amplitude of librations and τc is their characteristic time, is obtained by comparison of the 1/ Tm phase-relaxation rates at X- and Q-band EPR frequencies. We study three soft matrixes, viz., glassy trehalose and two ionic liquids, using TAMs with optimized relaxation properties OX063D and a dodeca- n-butyl homologue of Finland trityl (DBT). The motional parameters ⟨α2⟩τc obtained using TAMs are in excellent agreement with those obtained by means of nitroxide radicals. At the same time, the new TAM-based approach has (1) greater sensitivity due to the narrower EPR spectrum and (2) greater measuring accuracy and broader temperature range due to longer relaxation times. The developed approach may be fruitfully implemented to probe low-temperature molecular motions of TAM-labeled biopolymers, membrane systems, polymers, molecules in glassy media, and ionic liquids.