Frequency Electron Paramagnetic Resonance Research Articles

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.

A nondestructive method of identifying pigments on canvas using low frequency electron paramagnetic resonance spectroscopy

ABSTRACTElectron paramagnetic resonance (EPR) spectroscopy is a useful analytical tool for studying objects with cultural heritage significance. It is generally thought of as a destructive spectroscopy, owing to the small sample size, and thus not used to study paintings. We demonstrate that a form of this spectroscopy known as low frequency EPR spectroscopy can be used to nondestructively identify ultramarine blue, Egyptian blue, Han blue, rhodochrosite, blue vitriol, terracotta red, charcoal, and coal pigments in a linseed oil paint on canvas.

Tabletop 700 MHz electron paramagnetic resonance imaging spectrometer.

Low frequency electron paramagnetic resonance imaging is a powerful tool to non-invasively measure the physiological status of tumors. Here, we report on the design and functionality of a rapid scan and pulse table-top imaging spectrometer based around an arbitrary waveform generator and 25mm cross-loop resonator operating at 700 MHz. Two and four-dimensional rapid scan spectral-spatial images are presented. This table-top imager is a prototype for future pre-clinical imagers.

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes.

The electronic and magnetic properties of a set of mononuclear terbium(III) and dysprosium(III) complexes with two tetradentate 1-hydroxy-pyridin-2-one (1,2-HOPO) ligands are reported. Two primary coordination geometries are observed, depending on the length of the linker between the 1,2-HOPO donor moieties and the resulting arrangements of the linker. Fine details of the magnetic circular dichroism (MCD) spectra of the dysprosium(III) complexes illustrate differences in the splitting of the J multiplets and allow for a thorough ligand field analysis. High frequency electron paramagnetic resonance (HF-EPR) studies of the terbium(III) complexes give insight into the composition of the ground states. Ab initio calculations are utilized to rationalize the experimental results and further illustrate the effect of the structural features on the electronic and magnetic properties of the different complexes.

Verdazyl-ribose: A new radical for solid-state dynamic nuclear polarization at high magnetic field

Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants.

Development of Millimeter Wave Fabry-Pérot Resonator for Simultaneous Electron-Spin and Nuclear Magnetic Resonance Measurement

We report a Fabry-Perot resonator with spherical and flat mirrors to allow simultaneous electron-spin resonance (ESR) and nuclear magnetic resonance (NMR) measurements that could be used for double magnetic resonance (DoMR). In order to perform simultaneous ESR and NMR measurements, the flat mirror must reflect millimeter wavelength electromagnetic waves and the resonator must have a high Q value (Q > 3000) for ESR frequencies, while the mirror must simultaneously let NMR frequencies pass through. This requirement can be achieved by exploiting the difference of skin depth for the two frequencies, since skin depth is inversely proportional to the square root of the frequency. In consideration of the skin depth, the optimum conditions for conducting ESR and NMR using a gold thin film are explored by examining the relation between the Q value and the film thickness. A flat mirror with a gold thin film was fabricated by sputtering gold on an epoxy plate. We also installed a Helmholtz radio frequency coil for NMR and tested the system both at room and low temperatures with an optimally thick gold film. As a result, signals were obtained at 0.18 K for ESR and at 1.3 K for NMR. A flat-mirrored resonator with a thin gold film surface is an effective way to locate NMR coils closer to the sample being examined with DoMR.

Angle-dependent electron spin resonance of [formula omitted] measured with planar microwave resonators and in-situ rotation

We present a new experimental approach to investigate the magnetic properties of the anisotropic heavy-fermion system YbRh2Si2 as a function of crystallographic orientation. Angle-dependent electron spin resonance (ESR) measurements are performed at a low temperature of 1.6K and at an ESR frequency of 4.4GHz utilizing a superconducting planar microwave resonator in a 4He-cryostat in combination with in-situ sample rotation. The obtained ESR g-factor of YbRh2Si2 as a function of the crystallographic angle is consistent with results of previous measurements using conventional ESR spectrometers at higher frequencies and fields. Perspectives to implement this experimental approach into a dilution refrigerator and to reach the magnetically ordered phase of YbRh2Si2 are discussed.

An electron paramagnetic resonance mobile universal surface explorer

Many samples cannot be studied by electron paramagnetic resonance (EPR) spectroscopy because they are too large to fit into the spectrometer and too precious to be destructively sampled for study. An EPR mobile universal surface explorer (MOUSE), also known as a unilateral EPR spectrometer, was constructed for studying this class of sample. The EPR MOUSE can nondestructively record a low frequency EPR (LFEPR) spectrum of a small region of any size object by placing the MOUSE against the object. The capabilities of the EPR MOUSE are demonstrated on paramagnetic paint pigments on canvas, magnetic ink on paper, and a ceramic candlestick. The mobile nature of the MOUSE will allow the spectrometer to be brought to the sample, thus opening new applications of EPR spectroscopy.

A wide‐line low frequency electron paramagnetic resonance spectrometer

AbstractA continuous wave, homodyne, low frequency electron paramagnetic resonance spectrometer is described which can accommodate 15 cm diameter objects. The spectrometer can utilize small volume and surface coil probes operating between 100 and 500 MHz. The magnetic field can be scanned between 0 and 35 mT and is thus suitable for g < 2 spins and wide absorption lines. The spectrometer can record conventional field swept, field cycled, and spatially resolved spectra. Details of the instrument design and representative spectra from six different samples are presented. This design has applications to study objects with cultural heritage significance.

Room temperature ferromagnetic‐like response in “bulk” Y‐doped CeO2

Strong ferromagnetic‐like response is observed at room temperature in “bulk”‐ and nano‐crystalline Y‐doped CeO2. The saturation magnetization for “bulk” (∼600 nm) crystallites of CeO2 doped with 25 at.% Y is more than an order of magnitude higher compared to its nanocrystalline (∼10 nm) counterpart. High frequency electron spin resonance and 89Y nuclear magnetic resonance measurements indicate clustering of electronic defects in the “bulk” crystallites. The remarkable size dependence of the magnetic behavior likely originates from a collective magnetic response of defect‐lined nanodomain interfaces in the “bulk” crystallites, consistent with the giant orbital paramagnetism model.

A single-atom quantum memory in silicon

Long coherence times and fast gate operations are desirable but often conflicting requirements for physical qubits. This conflict can be resolved by resorting to fast qubits for operations, and by storing their state in a ‘quantum memory’ while idle. The 31P donor in silicon comes naturally equipped with a fast qubit (the electron spin) and a long-lived qubit (the 31P nuclear spin), coexisting in a bound state at cryogenic temperatures. Here, we demonstrate storage and retrieval of quantum information from a single donor electron spin to its host phosphorus nucleus in isotopically enriched 28Si. The fidelity of the memory process is characterised via both state and process tomography. We report an overall process fidelity %, and memory storage times up to 80 ms. These values are limited by a transient shift of the electron spin resonance frequency following high-power radiofrequency pulses.

ESR study of p-type natural 2H-polytype MoS2 crystals: The As acceptor activity

Low-temperature (T = 1.7–77 K) multi frequency electron spin resonance (ESR) study on p-type 2H-polytype geological MoS2 crystals reveals p-type doping predominantly originating from As atoms substituting for S sites in densities of (2.4 ± 0.2) × 1017 cm−3. Observation of a “half field”(g ∼ 3.88) signal firmly correlating with the central Zeeman As accepter signal indicates the presence of spin S > ½ As agglomerates, which together with the distinct multicomponent makeup of the Zeeman signal points to manifest non-uniform As doping; only ∼13% of the total As response originates from individual decoupled As dopants. From ESR monitoring the latter vs. T, an activation energy Ea = (0.7 ± 0.2) meV is obtained. This unveils As as a noticeable shallow acceptor dopant, appropriate for realization of effective p-type doping in targeted 2D MoS2-based switching devices.

Magnetic studies reveal near-perfect paramagnetism in the molecular semiconductor vanadyl phthalocyanine (C32H16N8VO)

Temperature (0.5–300K) and magnetic field (H up to 90kOe) dependences of the magnetization (M) of a powder sample of vanadyl phthalocyanine (VOPc) having the Phase II-triclinic structure are measured and analyzed. The data of χ = M/H vs. T measured in H = 1kOe fit the modified Curie-Weiss (CW) law, χ = χo+C/(T−θ), with C = 6.266×10−4 emuK/gOe, θ = −0.1K and χo = −9.3×10−7emu/gOe. The Curie constant C yields magnetic moment μ = 1.704μB, S = 1/2, and g = 1.967 characteristic of VO2+. The magnitude of θ = −0.1K signifying very weak inter-ion antiferromagnetic exchange coupling is supported by the analysis of the variable frequency (9.8–336GHz) electron paramagnetic resonance data. The isothermal data of M vs. H at ten temperatures between 0.5K and 300K when plotted as M vs. H/(T+0.1) collapses on to a single curve given by M = Motanh {gμBH/[2kB(T+0.1)]} with Mo = NgμBS = 9.48emu/g expected for S = 1/2 system, thus signifying near perfect paramagnetism in VOPc.

Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla

Abstract Dynamic nuclear polarization (DNP) is a methodology to increase the sensitivity of nuclear magnetic resonance (NMR) spectroscopy. It relies on the transfer of the electron spin polarization from a radical to coupled nuclear spins, driven by microwave excitation resonant with the electron spin transitions. In this work we explore the potential of pulsed multi-frequency microwave excitation in liquids. Here, the relevant DNP mechanism is the Overhauser effect. The experiments were performed with TEMPOL radicals in aqueous solution at room temperature using a Q-band frequency (1.2 T) electron paramagnetic resonance (EPR) spectrometer combined with a Minispec NMR spectrometer. A fast arbitrary waveform generator (AWG) enabled the generation of multi-frequency pulses used to either sequentially or simultaneously excite all three 14N-hyperfine lines of the nitroxide radical. The multi-frequency excitation resulted in a doubling of the observed DNP enhancements compared to single-frequency microwave excitation. Q-band free induction decay (FID) signals of TEMPOL were measured as a function of the excitation pulse length allowing the efficiency of the electron spin manipulation by the microwave pulses to be extracted. Based on this knowledge we could quantitatively model our pulsed DNP enhancements at 1.2 T by numerical solution of the Bloch equations, including electron spin relaxation and experimental parameters. Our results are in good agreement with theoretical predictions. Whereas for a narrow and homogeneous single EPR line continuous wave excitation leads to more efficient DNP enhancements compared to pulsed excitation for the same amount of averaged microwave power. The situation is different for radicals with several hyperfine lines or in the presence of inhomogeneous line broadening. In such cases pulsed single/multi-frequency excitation can lead to larger DNP enhancements.

Hyperpolarization of Frozen Hydrocarbon Gases by Dynamic Nuclear Polarization at 1.2 K.

We report a simple and general method for the hyperpolarization of condensed gases by dynamic nuclear polarization (DNP). The gases are adsorbed in the pores of structured mesoporous silica matrices known as HYPSOs (HYper Polarizing SOlids) that have paramagnetic polarizing agents covalently bound to the surface of the mesopores. DNP is performed at low temperatures and moderate magnetic fields (T = 1.2 K and B0 = 6.7 T). Frequency-modulated microwave irradiation is applied close to the electron spin resonance frequency (f = 188.3 GHz), and the electron spin polarization of the polarizing agents of HYPSO is transferred to the nuclear spins of the frozen gas. A proton polarization as high as P((1)H) = 70% can be obtained, which can be subsequently transferred to (13)C in natural abundance by cross-polarization, yielding up to P((13)C) = 27% for ethylene.

Dynamic nuclear polarization-magnetic resonance imaging at low ESR irradiation frequency for ascorbyl free radicals.

Highly water-soluble ubiquinone-0 (CoQ0) reacts with ascorbate monoanion (Asc) to mediate the production of ascorbyl free radicals (AFR). Using aqueous reaction mixture of CoQ0 and Asc, we obtained positively enhanced dynamic nuclear polarization (DNP)-magnetic resonance (MR) images of the AFR at low frequency (ranging from 515 to 530 MHz) of electron spin resonance (ESR) irradiation. The shape of the determined DNP spectrum was similar to ESR absorption spectra with doublet spectral peaks. The relative locational relationship of spectral peaks in the DNP spectra between the AFR (520 and 525 MHz), 14N-labeled carbamoyl-PROXYL (14N-CmP) (526.5 MHz), and Oxo63 (522 MHz) was different from that in the X-band ESR spectra, but were similar to that in the 300-MHz ESR spectra. The ratio of DNP enhancement to radical concentration for the AFR was higher than those for 14N-CmP, Oxo63, and flavin semiquinone radicals. The spectroscopic DNP properties observed for the AFR were essentially the same as those for AFR mediated by pyrroloquinoline quinone. Moreover, we made a success of in vivo DNP-MR imaging of the CoQ0-mediated AFR which was administered by the subcutaneous and oral injections as an imaging probe.

Assessing long-term habitability at an eastern Sahara oasis: ESR dating of molluscs and herbivore teeth at Dakhleh Oasis, Egypt

In the northeastern Sahara, electron spin resonance (ESR) dating of when animals lived documents their habitability in Dakhleh Oasis, Egypt. A Middle Pleistocene paleolake(s) covered >1700 km2. At eastern Locality Dak348, 10 m thick, remnant lacustrine marls yielded Pleistocene fauna, rare artefacts, and plant casts. No obvious unconformity exists within these deposits. From upper horizons, a hartebeest tooth ESR dated at 195 ± 11 ka, correlates with Marine Isotope Stage (MIS) 7, while molluscs from a stratigraphically higher horizon averaged 89 ± 10 ka, correlating with MIS 5a/b. At western Locality Dak006, upslope deflation has left a temporally mixed surficial lag. Numerous lagged tooth fragments, independently dated by ESR, correlate with MIS 5 through 17. Fragments from a slope sand unit correlate with MIS stages 3 through 6. One bovid tooth associated with Younger Middle Stone Age artefacts in the base of the sand dated at 84 ± 7 ka (MIS 5a/b). Molluscs from Romano-Byzantine backdirt at a breached artesian vent dated to 8–15 ± 1 ka, suggesting that ponds formed during MIS 1 and 2. Even without well defined sedimentary contexts, ESR frequency data indicate that the oasis was habitable for herbivores during at least twelve stages in the Mid-Late Quaternary, and, therefore, likely also for humans.

Low Frequency EPR and EMR Point Spectroscopy and Imaging of a Surface

Low frequency electron paramagnetic resonance (LFEPR) spectrometers operating between 100 and 500 MHz typically have large-volume magnets that accommodate large samples. LFEPR spectroscopy with a 2.9 mm diameter surface coil was used to record point spectra and image the spatial distribution of the spin probe 2,2-Diphenyl-1-picrylhydrazyl (DPPH) and electrophotographic toner in printed letters on a flat surface. The location of the surface coil was fixed on the desired location when a spectrum was recorded. The magnetic field of the spectrometer was fixed on the location of the signal and the sample was scanned under the surface coil in parallel trajectories to produce an image of the signal in the letters “LFEPR”. We speculate on the utility of this technique to study flat objects such as paintings and illuminated manuscripts with cultural heritage significance.

Intrinsic and extrinsic defects in a family of coal-derived graphene quantum dots

In this letter, we report on the high frequency (239.2 and 336 GHz) electron spin resonance (ESR) studies performed on graphene quantum dots (GQDs), prepared through a wet chemistry route from three types of coal: (a) bituminous, (b) anthracite, and (c) coke; and from non-coal derived GQDs. The microwave frequency-, power-, and temperature-dependent ESR spectra coupled with computer-aided simulations reveal four distinct magnetic defect centers. In bituminous- and anthracite-derived GQDs, we have identified two of them as intrinsic carbon-centered magnetic defect centers (a broad signal of peak to peak width = 697 (10−4 T), g = 2.0023; and a narrow signal of peak to peak width = 60 (10−4 T), g = 2.003). The third defect center is Mn2+ (6S5/2, 3d5) (signal width = 61 (10−4 T), g = 2.0023, Aiso = 93(10−4 T)), and the fourth defect is identified as Cu2+ (2D5/2, 3d9) (g⊥ = 2.048 and g‖ = 2.279), previously undetected. Coke-derived and non-coal derived GQDs show Mn2+ and two-carbon related signals, and no Cu2+ signal. The extrinsic impurities most likely originate from the starting coal. Furthermore, Raman, photoluminescence, and ESR measurements detected no noticeable changes in the properties of the bituminous GQDs after one year. This study highlights the importance of employing high frequency ESR spectroscopy in identifying the (magnetic) defects, which are roadblocks for spin relaxation times of graphene-based materials. These defects would not have been possible to probe by other spin transport measurements.