Electron Paramagnetic Resonance Line Research Articles

P1 Center Electron Spin Clusters Are Prevalent in Type Ib Diamonds.

Understanding the spatial distribution of the P1 centers is crucial for diamond-based sensors and quantum devices. P1 centers serve as polarization sources for dynamic nuclear polarization (DNP) quantum sensing and play a significant role in the relaxation of nitrogen vacancy (NV) centers. Additionally, the distribution of NV centers correlates with the distribution of P1 centers, as NV centers are formed through the conversion of P1 centers. We utilized DNP and pulsed electron paramagnetic resonance (EPR) techniques that revealed strong clustering of a significant population of P1 centers that exhibit exchange coupling and produce asymmetric line shapes. The 13C DNP frequency profile at a high magnetic field revealed a pattern that requires an asymmetric EPR line shape of the P1 clusters with electron-electron (e-e) coupling strengths exceeding the 13C nuclear Larmor frequency. EPR and DNP characterization at high magnetic fields was necessary to resolve energy contributions from different e-e couplings. We employed a two-frequency pump-probe pulsed electron double resonance technique to show cross-talk between the isolated and clustered P1 centers. This finding implies that the clustered P1 centers affect all of the P1 populations. Direct observation of clustered P1 centers and their asymmetric line shape offers a novel and crucial insight into understanding magnetic noise sources for quantum information applications of diamonds and for designing diamond-based polarizing agents with optimized DNP efficiency for 13C and other nuclear spins of analytes. We propose that room temperature 13C DNP at a high field, achievable through straightforward modifications to existing solution-state NMR systems, is a potent tool for evaluating and controlling diamond defects.

Alteration in the molecular structure of the adenine base exposed to gamma irradiation: An ESR study

Abstract Adenine polycrystals were obtained from their powder form under effective crystallization conditions by adjustment of the concentration of chemical solutions. The adenine samples were irradiated with a 60Co gamma-ray source at room temperature for 12, 24, 48, and 72 h, and then these samples were investigated between 240 and 400 K using an electron spin resonance (ESR) spectrometer. No signals were observed in the non-irradiated samples irradiated for 12, 24, and 48 h; however, when irradiated for 72 h, the samples exhibited complex ESR spectra. The analysis indicated the presence of a radical structure, NH ̇ \dot{{NH}} . The hyperfine splitting and g-values were calculated from the spectra by simulation programs. Also, during the measurements, it was observed that the shapes of the ESR lines changed slightly with the temperature.

Charge Distribution Patterns of IA3 Impact Conformational Expansion and Hydration Diffusivity of the Disordered Ensemble.

IA3 is a 68 amino acid natural peptide/protein inhibitor of yeast aspartic proteinase A (YPRA) that is intrinsically disordered in solution with induced N-terminal helicity when in the protein complex with YPRA. Based on the intrinsically disordered protein (IDP) parameters of fractional net charge (FNC), net charge density per residue (NCPR), and charge patterning (κ), the two domains of IA3 are defined to occupy different domains within conformationally based subclasses of IDPs, thus making IA3 a bimodal domain IDP. Site-directed spin labeling (SDSL) electron paramagnetic resonance (EPR) spectroscopy and low-field Overhauser dynamic nuclear polarization (ODNP) spectroscopy results show that these two domains possess different degrees of compaction and hydration diffusivity behavior. This work suggests that SDSL EPR line shapes, analyzed in terms of their local tumbling volume (VL), provide insights into the compaction of the unstructured IDP ensemble in solution and that protein sequence and net charge distribution patterns within a conformational subclass can impact bound water hydration dynamics, thus possibly offering an alternative thermodynamic property that can encode conformational binding and behavior of IDPs and liquid-liquid phase separations.

Evidence of ferromagnetic coupling for manganese pairs in a layered van der Waals GaS semiconductor

Using high-frequency electron paramagnetic resonance (EPR), we have observed the ferromagnetic coupling of manganese Mn2+ pairs in a layered van der Waals GaS semiconductor. The EPR spectra of Mn2+ pairs (Mn24+) [replacing covalently bonded Ga24+ pairs oriented along the chain axis (c axis) of two gallium ions and being situated in the center of the layer] were recorded at 94 and 130 GHz. The fine structure parameters for the lower multiplets with spin S = 5 and S = 4 were determined equal to D = −0.040 cm−1 and D ≅ −0.035 cm−1, respectively. Based on the observation of additional EPR lines in the region of intersection of the levels in the magnetic field of the multiplet with S = 5 and S = 4, the energy of the isotropic exchange interaction J was estimated to be ∼−0.5 cm−1. For all transitions, a well-resolved hyperfine structure was observed, due to the interaction with two equivalent 55Mn nuclei, leading to the appearance of 11 lines with a hyperfine interaction constant A = 30(1) × 10−4 cm−1, which is approximately half the hyperfine interaction constant for single Mn2+ ions. In addition, a signal from single manganese ions Mn2+ with spin S = 5/2 and a hyperfine interaction constant A = 60(1) × 10−4 cm−1 was observed, which are characterized by extremely large fine structure splitting of D = −0.15 cm−1. Simultaneously with EPR studies, the crystals were monitored by photoluminescence and micro-Raman scattering measurements using a microscope with confocal optics.

Conditions for EPR detection of chirality-induced spin selectivity in spin-polarized radical pairs in isotropic solution.

Chiral molecules can act as spin filters, preferentially transmitting electrons with spins polarized along their direction of travel, an effect known as chirality-induced spin selectivity (CISS). In a typical experiment, injected electrons tunnel coherently through a layer of chiral material and emerge spin-polarized. It is also possible that spin polarization arises in radical pairs formed photochemically when electrons hop incoherently between donor and acceptor sites. Here we aim to identify the magnetic properties that would optimise the visibility of CISS polarization in time-resolved electron paramagnetic resonance (EPR) spectra of transient radical pairs without the need to orient or align their precursors. By simulating spectra of actual and model systems, we find that CISS contributions to the polarization should be most obvious when at least one of the radicals has small g-anisotropy and an inhomogeneous linewidth larger than the dipolar coupling of the two radicals. Under these conditions there is extensive cancellation of absorptive and emissive enhancements making the spectrum sensitive to small changes in the individual EPR line intensities. Although these cancellation effects are more pronounced at lower spectrometer frequencies, the spectral changes are easier to appreciate with the enhanced resolution afforded by high-frequency EPR. Consideration of published spectra of light-induced radical pairs in photosynthetic bacterial reaction centres reveals no significant CISS component in the polarization generated by the conventional spin-correlated radical pair mechanism.

Electron paramagnetic resonance of VN–VGa complex in BGaN

A metastable photoinduced electron paramagnetic resonance (EPR) signal at low temperatures is reported for GaN alloyed with boron (i.e., BxGa1−xN) epitaxial layers grown at temperatures ranging from 840 to 1090° C. An isotropic EPR line with g = 2.004 is observed with an intensity depending on the growth temperature for all the samples with boron content between 0.73% and 2.51%. The temperature dependence of EPR intensities is compared with the results of high-resolution photoinduced transient spectroscopy. This enables a link between particular traps and the EPR signal. The activation energies of these traps are consistent with the theoretical position of the VN–VGa complex. Thermal annihilation of the EPR signal with 30 meV activation energy corresponds to shallow donor ionization. A model explaining the light-induced EPR signal that involves redistribution of electrons between deep and shallow donors, mediated by photoionization to the conduction band, is proposed.

EPR Spectrum Analysis of DPPH and MnCl2

This paper presents the findings of electron paramagnetic resonance (EPR) spectroscopy experiments conducted on two different samples: 2,2-diphenyl-1-picrylhydrazyl (DPPH) and Manganese Chloride (MnCl2) dissolved in H2O. The experiments were conducted at Dr. D. Petasis EPR lab located in Allegheny College, Meadville, PA, USA. A Varian X-Band spectrometer was utilized for the analysis of the EPR absorption spectra. The primary objective was to determine the g-values and hyperfine structure of the two samples, which can be crucial in characterizing their electronic properties. The g-values obtained for both DPPH and MnCl2 were found to be remarkably close to the theoretically calculated values, suggesting the high accuracy and success of the experiments. This agreement validates the reliability of the EPR measurements and demonstrates the precision of the instruments and experimental procedures employed. For the MnCl2 sample, a hyperfine structure with 6 visible EPR lines was observed. By analyzing the number of EPR lines, the nuclear spin of the Mn(II) ion was determined to be I = 5/2, consistent with the expected value for Mn(II). The hyperfine constant (A) was also calculated from the field position differences between adjacent lines, providing further insights into the sample's magnetic properties. Comparisons were made between the obtained g-values and hyperfine constant with the expected values for Mn(II) in the literature, confirming the accuracy of the measurements and reinforcing the credibility of the experimental data. Overall, the EPR spectroscopy experiments conducted on DPPH and MnCl2 in H2O have provided valuable information about the electronic and magnetic properties of these paramagnetic materials. The results demonstrate the effectiveness of EPR spectroscopy as a powerful experimental technique for investigating various bio-chemical samples and understanding the effects of solvents on the EPR spectra of compounds. The close agreement between the experimental and theoretical values for the g-factors and hyperfine constants reinforces the reliability of the data obtained from the EPR experiments.

Phase Composition and Magnetic Properties of Nanoparticles with Magnetite–Maghemite Structure

Precipitation of nanopowders with mixed magnetite–maghemite composition was carried out under different conditions and with different separation techniques. The exact character of interactions of different iron oxide phases in the nanopowder was the main object of interest. The obtained nanopowders have spherical particles about 10–20 nm in size. Electron paramagnetic resonance (EPR) study showed that iron ions incorporate fully into magnetite and maghemite structures. The shape of the EPR line points out that single homogenous solid solutions were formed during synthesis. In the studied solid solutions, different ratios of vacancies and Fe2+/Fe3+ ratios were observed but in spite of different synthesis techniques in both cases, there were no additional diamagnetic structural phases presented.

Temperature effects in EPR spectra and optical features of plastically deformed natural IaAB, IaB, and low-nitrogen diamonds

In this study, the three natural IaB, IaAB, and low-nitrogen diamond crystals from Yakutian province with plastic deformation characteristic features have been investigated. It is shown that for low-nitrogen and type IaB diamonds, plastic deformation does not lead to brown coloration raising the question about the nature of the color. The crystal of the IaAB type is brown and contains from 53 to 64 % of the total nitrogen in the form of A-aggregates. In electron paramagnetic resonance (EPR), this sample reveals the W7 centers which are formed from the A-centers as a result of plastic deformation and the 490.7 single line related to dangling bonds in the dislocation cores. For this brown plastically deformed diamond the narrowing of the 490.7 EPR line and the dynamical broadening of the W7 lines are observed with a temperature increase from 77 to 300 K. It is assumed that the charge transfer from the W7 defects to dangling bonds in the dislocation core takes place. The obtained changes in the linewidths of EPR spectra can be explained by the mobility of electrons localized on dangling carbon bonds where the varying polarization of the W7 orbitals leads to the modulation of the nitrogen hyperfine structure. In this case, the charge-transfer complexes formed can be responsible for the appearance of the 550 nm band in the optical absorption spectra and, as a consequence, for the brown color of the plastically deformed IaAB diamond sample.

Random singlets in the s=5/2 coupled frustrated cubic lattice Lu3Sb3Mn2O14

We combine thermodynamic, electron spin resonance (ESR), and muon spin-relaxation ($\mathrm{\ensuremath{\mu}}\mathrm{SR}$) measurements with density functional theory (DFT) and classical Monte Carlo calculations toward understanding a disorder-driven behavior of the 3D coupled frustrated cubic lattice $\mathrm{Lu}{}_{3}\mathrm{Sb}{}_{3}\mathrm{Mn}{}_{2}{\mathrm{O}}_{14}$ with $s=5/2$. The classical Monte Carlo calculations based on exchange interactions extracted from DFT predict that $\mathrm{Lu}{}_{3}\mathrm{Sb}{}_{3}\mathrm{Mn}{}_{2}{\mathrm{O}}_{14}$ undergoes a transition to magnetic ordering. In sharp contrast, our specific heat measurements evince a weak magnetic anomaly at 0.5 K while $\mathrm{\ensuremath{\mu}}\mathrm{SR}$ detects neither long-range magnetic order nor spin freezing down to 0.3 K. For temperatures above 2 K, our $\mathit{ac}$ susceptibility, magnetization, and specific heat data obey temperature-magnetic field scalings, indicative of the formation of 3D random singlets. The development of multiple ESR lines with decreasing temperature below 80 K supports the notion of inhomogeneous magnetism. Our results extend random-singlet physics to 3D frustrated classical magnets with a large spin number $s=5/2$.

Electron and nuclear magnetic properties near ZEFOZ region

In the vicinity of spin level anti-crossings, electron-nuclear spin systems reveal characteristic features that have been investigated by electron paramagnetic resonance (EPR) methods, including electron spin echo envelope modulation (ESEEM). The spectral properties depend considerably on the difference, ΔB, between the magnetic field and the critical field at which the zero first-order Zeeman shift (ZEFOZ) occurs. To analyze the characteristic features near the ZEFOZ point, analytical expressions for the behavior of EPR spectra and ESEEM traces as a function of ΔB are obtained. It is shown that the influence of hyperfine interactions (HFI) decreases linearly when approaching the ZEFOZ point. The HFI splitting of the EPR lines is essentially independent of ΔB near the ZEFOZ point, while the depth of the ESEEM signal has an approximately quadratic dependence on ΔB with a small cubic asymmetry due to the Zeeman interaction of the nuclear spin.

Resolving Complex Photoconductivity of Perovskite and Organic Semiconductor Films Using Phase-Sensitive Microwave Interferometry

Complex transient photoconductivity (Δσ) contains rich fingerprints of charge recombination dynamics in photoactive films. However, a direct measure of both real (Δσ′) and imaginary (Δσ″) components has proven difficult using conventional cavity-based time-resolved microwave conductivity approaches. Here, we present a novel approach to resolve Δσ′ and Δσ″ parts of Δσ by using a nonresonant coplanar transmission line and a microwave interferometric detection scheme. The use of a phase-sensitive microwave interferometer greatly increases the measurement sensitivity and eliminates the requirement of a resonant cavity. This broadband detection scheme allows for direct measurement of Δσ. The relationship between the experimental phase shift and Δσ′ and Δσ″ components is decoded through an in situ electron spin resonance (ESR) measurement. ESR line shape analysis is used to confirm the assignment of the transients to the Δσ′ and Δσ″ components. We demonstrate the utility of this technique on thin films of poly(3-hexylthiophene): [6,6]-phenylC61-butyric acid methyl ester (P3HT:PCBM) and perovskite MA0.85FA0.15PbI3 films on glass.

D 6 h Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

<i>D</i> ^{6 <i>h</i>} Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

Chemical Gardens Mimic Electron Paramagnetic Resonance Spectra and Morphology of Biogenic Mn Oxides.

Manganese (Mn) oxides are ubiquitous in nature and occur as both biological and abiotic minerals, but empirically distinguishing between the two remains a problem. Recently, electron paramagnetic resonance (EPR) spectroscopy has been proposed for this purpose. It has been reported that biogenic Mn oxides display a characteristic narrow linewidth in contrast to their pure abiotic counterparts, which is explained in part by the large number of cation vacancies that form within the layers of biogenic Mn oxides. It was, therefore, proposed that natural samples that display a narrow EPR linewidth, ΔHpp < 580G, could be assigned to a biogenic origin. However, in poorly crystalline or amorphous solids, both dipolar broadening and exchange narrowing simultaneously determine the linewidth. Considering that the spectral linewidth is governed by several mechanisms, this approach might be questioned. In this study, we report synthetic chemical garden Mn oxide biomorphs that exhibit both morphologically life-like structures and narrow EPR linewidths, suggesting that a narrow EPR line may be unsuitable as reliable evidence in assessment of biogenicity.

Microstructure and Conduction Electron Quantum Properties of Small Diamond Cubic α-Sn Nanocrystals Embedded in Cubic Boron Nitride Crystals.

The morphology, structure, composition, and conduction electron properties of quasi-spherical tin nanocrystals (NCs) of 2.5 nm average diameter, with unstrained, bulk-like α-Sn diamond cubic structure, observed in dark cubic boron nitride (cBN) crystallites, were determined by correlated analytical high-resolution scanning transmission electron microscopy and multifrequency electron spin resonance (ESR) investigations. The narrow Lorentzian ESR line with g = 2.0028 is attributed to the conduction ESR of the α-Sn NCs, consistent with the temperature- and frequency-independent small g-shift and intensity reduction under high temperature (950 °C) vacuum annealing when the α-Sn NCs are thermally dissolved in the host cBN crystallites. The ESR linewidth and line intensity vs temperature dependences recorded in the 20 to 295 K range are quantitatively described considering the presence of discrete, quantum confinement-induced conduction electron energy levels with ΔQC/k B = 125 K separation, close to the theoretical value for conductive α-Sn NCs of 2.5 nm in diameter. The observed properties are tentatively explained with the predicted nanosize induced band-gap opening and change of band ordering from bulk α-Sn to small unstrained α-Sn NCs, resulting in a topological phase transition that also explains the predominantly s-like character of the conduction band electron orbitals.

RF simulation platform of qubit control using FDSOI technology for quantum computing

In this paper, we report on simulations of an Electron Spin Resonance (ESR) RF control line for semiconductor electron spin qubits. The simulation includes both the ESR line characteristics (geometry and configuration, stack and material properties) and the electromagnetic (EM) environment at the vicinity of the qubits such as gates and interconnect network. With the accurate assessment of the magnetic and electric field distribution, we found that the EM environment of the qubits contributes significantly to the ESR line efficiency for spin control characterized by the magnetic over electric field ratio generated at the qubit location.

Continuous wave and pulsed EPR study of Cd1-xMnxTe crystals with different Mn content

The cadmium manganese telluride (Cd1–xMnxTe) crystals (x &lt; 0.001 and x = 0.02, 0.04, 0.1) grown using the Bridgman method were studied by applying continuous wave and pulsed electron paramagnetic resonance (EPR) spectroscopy in the wide temperature range. The Cd1–xMnxTe crystals with x &lt; 0.001 revealed the EPR spectrum from isolated Mn2+ with g⊥ = g∥ = 2.0074(3), |A⊥| = |A∥| = 56.97 ⋅ 10–4 cm–1, |a| = 30.02⋅10–4 cm–1, while Cd1–xMnxTe crystals with x = 0.02…0.04 are characterized by two single broad isotropic EPR lines of Lorentzian shape (g ~ 2.009 and g ~ 1.99) due to Mn clusters of different sizes. The EPR spectrum of Cd1–xMnxTe crystals with x = 0.01 consists of the single broad line at g ~ 2.01 due to higher level of homogeneity inherent to these crystals. The temperature dependence of spin relaxation times for the isolated Mn2+ center in the Cd1–xMnxTe crystals with x &lt; 0.001 has been described using the conceptions of Orbach process for TM–1 and two-phonon Raman process for T1–1.

Optical Properties and Light-Induced Charge Transfer in Selected Aromatic C60 Fullerene Derivatives and in Their Bulk Heterojunctions with Poly(3-Hexylthiophene).

Fullerene derivatives offer great scope for modification of the basic molecule, often called a buckyball. In recent years, they have been the subject of numerous studies, in particular in terms of their applications, including in solar cells. Here, the properties of four recently synthesized fullerene C60 derivatives were examined regarding their optical properties and the efficiency of the charge transfer process, both in fullerene derivatives themselves and in their heterojunctions with poly (3-hexylthiophene). Optical absorption, electron spin resonance (ESR), and time-resolved photoluminescence (TRPL) techniques were applied to study the synthesized molecules. It was shown that the absorption processes in fullerene derivatives are dominated by absorption of the fullerene cage and do not significantly depend on the type of the derivative. It was also found by ESR and TRPL studies that asymmetrical, dipole-like derivatives exhibit stronger light-induced charge transfer properties than their symmetrical counterparts. The observed inhomogeneous broadening of the ESR lines indicated a large disorder of all polymer–fullerene derivative blends. The density functional theory was applied to explain the results of the optical absorption experiments.

Domain-Specific Phase Transitions in a Supramolecular Nanostructure.

Understanding thermal phase behavior within nanomaterials can inform their rational design for medical technologies like drug delivery systems and vaccines, as well as for energy technologies and catalysis. This study resolves thermal phases of discrete domains within a supramolecular aramid amphiphile (AA) nanoribbon. Dynamics are characterized by X-band EPR spectroscopy of spin labels positioned at specific sites through the nanoribbon cross-section. The fitting of the electron paramagnetic resonance (EPR) line shapes reveals distinct conformational dynamics, with fastest dynamics at the surface water layer, intermediate dynamics within the flexible cationic head group domain, and slowest dynamics in the interior aramid domain. Measurement of conformational mobility as a function of temperature reveals first- and second-order phase transitions, with melting transitions observed in the surface and head group domains and a temperature-insensitive crystalline phase in the aramid domain. Arrhenius analysis yields activation energies of diffusion at each site. This work demonstrates that distinct thermal phase behaviors between adjacent nanodomains within a supramolecular nanostructure may be resolved and illustrates the utility of EPR spectroscopy for thermal phase characterization of nanostructures.

Polymer Nanocomposite Containing Palladium Nanoparticles: Synthesis, Characterization, and Properties.

Composite nanomaterials have been prepared through thermal decomposition of palladium diacetate. The composite contains palladium nanoparticles embedded in high-pressure polyethylene. The materials were studied by a number of different physico-chemical methods, such as transmission electron microscopy, X-ray diffraction, X-ray absorption spectroscopy, electron paramagnetic resonance, and EXAFS. The average size of the nanoparticles is 7.0 ± 0.5 nm. It is shown that with the decrease of metal content in the polymer matrix the average size of nanoparticles decreased from 7 to 6 nm, and the coordination number of palladium also decreased from 7 to 5.7. The mean size of palladium particles increases with the growing concentration of palladium content in the matrix. It is shown that the electrophysical properties of the material obtained depend on the filler concentration. The chemical composition of palladium components includes metallic palladium, palladium (III) oxide, and palladium dioxide. All samples have narrow lines (3–5 Oe) with a g factor of around two in the electron paramagnetic resonance (EPR) spectra. It is shown that EPR lines have uneven boarding by saturation lines investigation. The relaxation component properties are different for spectral components. It leads to the spectrum line width depending on the magnetic field value. At first approximation, the EPR spectra can be described as a sum of two Lorentzian function graphs, corresponding to the following two paramagnetic centers: one is on the surface, and one is inside the palladium particles. Some of the experimental characteristics were measured for the first time. The data obtained indicate interesting properties of palladium-based nanocomposites, which will be useful for obtaining products based on these materials.