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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. [ABSTRACT FROM AUTHOR]

Organic semiconductors (OSCs) are featured by weak spin-orbit coupling due to their light chemical element composition, which enables them to maintain spin orientation for a long spin lifetime and show significant potential in room-temperature spin transport. Carrier mobility and spin lifetime are the two main factors of the spin transport performance of OSCs, however, their ambiguous mechanisms with molecular structure make the development of spintronic materials really stagnant. Herein, the effects of halogen substitution in bay-annulated indigo-based polymers on carrier mobility and spin relaxation have been systematically investigated. The enhanced carrier mobility with an undiminished spin lifetime contributes to a 3.7-fold increase in spin diffusion length and a record-high magnetoresistance of 8.7% at room temperature. By analyzing the spin-orbit coupling and hyperfine interaction, it was found that the distance of the substitution site from the conjugated center and the nitrogen atoms in the molecules play crucial roles in spin relaxation. Based on the above results, we proposed a molecular design strategy of halogen substitution far from conjugate center to enhance spin transport efficiency, presenting a promising avenue for advancing the field of organic spintronics. The spin transport mechanism remains unclear for organic semiconductors. Here, authors investigate the effect of halogen substitution in bay-annulated indigo-based polymers and reveal the distance of substitution site from conjugated center and nitrogen atoms play crucial roles in spin relaxation. [ABSTRACT FROM AUTHOR]

Frequency-stabilized lasers are fundamental topics in research relating to optical frequency and wavelength standards. The absolute frequencies and hyperfine structures of the R(106)50-0, R(100)49-0, R(84)47-0, R(59)45-0, P(82)47-0, and P(71)46-0 lines of molecular iodine (127I2) at 514 nm were measured using a frequency-stabilized laser based on modulation transfer spectroscopy. The hyperfine splitting of each line was fitted to a four-term Hamiltonian with an uncertainty of several kilohertz to obtain the hyperfine constants for the line. A total of 97 hyperfine transitions of the six lines were measured with an uncertainty of 5.6 kHz (fractionally 9.6 × 10−12). They can provide new optical frequency references for telecommunication and other applications. [ABSTRACT FROM AUTHOR]

The paper provides a review and educational focus on the study of the hyperfine structure of the hydrogen atom, the exploration of which began in the middle of the last century. Since neutral hydrogen is the most common chemical element in the Universe, the radiation emitted due to the hyperfine splitting of its ground state allows for a wide observation of various astrophysical objects and the evolution of the Universe. Here, we describe the transition and calculate the average lifetime of the excited energy level within the hyperfine structure of the hydrogen atom. Additionally, we consider the influence of a magnetic field on the splitting and the average lifetime of the excited energy levels in this system. [ABSTRACT FROM AUTHOR]

Hydrogen chloride (HCl) is a key repository of chlorine in the interstellar medium. Accurate determinations of its abundance are critical to assessing the chlorine elemental abundance and constraining stellar nucleosynthesis models. To aid in modeling recent and future observations of HCl rovibrational spectra, we present cross sections and rate coefficients for collisions between HCl and molecular hydrogen. Transitions between rovibrational states of HCl are considered for temperatures ranging from 10 to 3000 K. Cross sections are computed using a full dimensional quantum close-coupling (CC) method and a reduced dimensionality coupled-states (CS) approach. The CS results, benchmarked against the CC results, are used with a recoupling approach to calculate hyperfine-resolved rate coefficients for rovibrational transitions of HCl induced by H2. The rate coefficients will allow for a better determination of the HCl abundance in the interstellar medium and an improved understanding of interstellar chlorine chemistry. We demonstrate the utility of the new rate coefficients in a nonthermodynamic equilibrium radiative transfer model applied to observations of HCl rovibrational transitions in a circumstellar shell. [ABSTRACT FROM AUTHOR]

The suppression of ferroquadrupolar order in TmVO4 in a magnetic field is well-described by the transverse field Ising model, enabling detailed studies of critical dynamics near the quantum phase transition. We describe nuclear magnetic resonance measurements in pure and Y-doped single crystals. The non-Kramers nature of the ground state doublet leads to a unique form of the hyperfine coupling that exclusively probes the transverse field susceptibility. Our results show that this quantity diverges at the critical field, in contrast to the mean-field prediction. Furthermore, we find evidence for quantum critical fluctuations present near Tm-rich regions in Y-doped crystals at levels beyond which long-range order is suppressed, suggesting the presence of quantum Griffiths phases. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We report the synthesis of three triphenylamine-based verdazyl radicals. These include a mono, bis, and tris(verdazyl) at the 4-position(s) of the N–Ar groups, containing one, two, and three unpaired electrons, respectively. Each of these compounds is air stable and fully characterized using EPR spectroscopy, high-resolution mass spectrometry, infrared spectroscopy, UV/Vis spectroscopy, and cyclic voltammetry. From the UV/Vis absorbance data, the optical absorbance energy gaps were found to be ∼2.35 eV for all three verdazyl-containing compounds. Cyclic voltammetry was used to estimate the energy levels of the singly occupied molecular orbitals, which are −4.91, −5.12, and −4.98 eV for mono, bis, and tris(verdazyl) compounds, respectively. Spin–spin exchange interactions were observed in the EPR spectra of both the bis and tris(verdazyl)s, leading to additional hyperfine coupling patterns and assignment of the ground states as triplet and quartet, respectively. [ABSTRACT FROM AUTHOR]

Liquid-liquid phase separation is the key process underlying formation of membrane-less compartments in cells. A highly dynamic cellular body with rapid component exchange is Cajal body (CB), which supports the extensive compositional dynamics of the RNA splicing machinery, spliceosome. Here, we select an arginine-glycine (RG)-rich segment of coilin, the major component of CB, establish its RNA-induced phase separation, and through combined use of nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) probes, interrogate its dynamics within the crowded interior of formed droplets. Taking advantage of glycine-based singlet-states, we show that glycines retain a large level of sub-nanoseconds dynamics inside the coilin droplets. Furthermore, the continuous-wave (CW) and electron-electron dipolar (PELDOR) and electron-nucleus hyperfine coupling EPR data (HYSCORE) support the RNA-induced formation of dynamic coilin droplets with high coilin peptide concentrations. The combined NMR and EPR data reveal the high dynamics of the RG-rich coilin within droplets and suggest its potential role in the large dynamics of CBs. The authors show the RNA-induced droplet formation by a component of Cajal bodies and reveal the large nanoseconds mobility of glycine residues inside droplets as a molecular factor potentially contributing to the large dynamics of Cajal bodies. [ABSTRACT FROM AUTHOR]

Highly resistant to reduction nitroxides open new opportunities for structural studies of biological macromolecules in their native environment inside living cells and for functional imaging of pH and thiols, enzymatic activity and redox status in living animals. 3,4-Disubstituted nitroxides of 2,2,5,5-tetraethylpyrrolidine and pyrroline series with a functional group for binding to biomolecules and a polar moiety for higher solubility in water and for more rigid attachment via additional coordination to polar sites were designed and synthesized. The EPR spectra, lipophilicities, kinetics of the reduction in ascorbate-containing systems and the decay rates in liver homogenates were measured. The EPR spectra of all 3,4-disubstituted pyrrolidine nitroxides showed additional large splitting on methylene hydrogens of the ethyl groups, while the spectra of similar pyrroline nitroxides were represented with a simple triplet with narrow lines and hyperfine structure of the nitrogen manifolds resolved in oxygen-free conditions. Both pyrrolidine and pyrroline nitroxides demonstrated low rates of reduction with ascorbate, pyrrolidines being a bit more stable than similar pyrrolines. The decay of positively charged nitroxides in the rat liver homogenate was faster than that of neutral and negatively charged radicals, with lipophilicity, rate of reduction with ascorbate and the ring type playing minor role. The EPR spectra of N,N-dimethyl-3,4-bis-(aminomethyl)-2,2,5,5-tetraethylpyrrolidine-1-oxyl showed dependence on pH with pKa = 3, ΔaN = 0.055 mT and ΔaH = 0.075 mT. [ABSTRACT FROM AUTHOR]

N-heterocycles are of special relevance in astrobiology but at present no nitrogen-containing heterocycles have been detected in the interstellar medium (ISM). Thus far, the simplest N-heterocyclic compound, 2H-Azirine (c-C2H3N), has not been conclusively identified, despite being searched for. Recently, several cyano and ethynyl derivatives of unsaturated hydrocarbons have been discovered in the cold prestellar core Taurus Molecular Cloud 1 (TMC-1). The purpose of this work is to assess the feasibility of the possible formation of cyano and ethynyl derivatives of azirine (c-C2H2N-CN, c-C2H2N-CCH) under interstellar conditions and provide high-level theoretical spectroscopic parameters of the most relevant cyano- and ethynyl-azirine isomers to facilitate their experimental identification. Six isomers are located for each, cyano- and ethynyl-azirine derivatives, and their interconversion processes are studied. The reactions of 2H-azirine with the CN or CCH radicals in the gas phase are explored as possible formation routes of cyano and ethynyl azirine. We found that the formation processes of the most stable isomers, namely 3-cyano-2H-azirine, 2-cyano-2H-azirine, 3-ethynyl-2H-azirine, and 2-ethynyl-2H-azirine, are exothermic and barrier free. Thus, these compounds stand out as potential targets to be searched for in space. Based on the newly determined rotational spectroscopic parameters, which also account for 14N hyperfine splittings, we compile a line catalogue for each system up to 50 GHz as a preliminary and required step to characterize these molecules experimentally, whether in the laboratory or directly in the ISM. [ABSTRACT FROM AUTHOR]

5-Deazaflavins are analogs of naturally occurring flavin cofactors. They serve as substitutes for natural flavin cofactors to investigate and modify the reaction pathways of flavoproteins. Demethylated 5-deazaflavins are potential candidates for artificial cofactors, allowing us to fine-tune the reaction kinetics and absorption characteristics of flavoproteins. In this contribution, demethylated 5-deazariboflavin radicals are investigated (1) to assess the influence of the methyl groups on the electronic structure of the 5-deazaflavin radical and (2) to explore their photophysical properties with regard to their potential as artificial cofactors. We determined the proton hyperfine structure of demethylated 5-deazariboflavins using photochemically induced dynamic nuclear polarization (photo-CIDNP) spectroscopy, as well as density functional theory (DFT). To provide context, we compare our findings to a study of flavin mononucleotide (FMN) derivatives. We found a significant influence of the methylation pattern on the absorption properties, as well as on the proton hyperfine coupling ratios of the xylene moiety, which appears to be solvent-dependent. This effect is enhanced by the replacement of N5 by C5-H in 5-deazaflavin derivatives compared to their respective flavin counterparts. [ABSTRACT FROM AUTHOR]

Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing with paramagnetic systems, several decades of research have led to the development of rule-of-the-thumb criteria for optimizing the experiments, allowing for the detection of nuclei that are in very close proximity to the metal center. In turn, the observation of these systems, coupled with the development of robust and accessible quantum chemical methods, is promising to provide a link between the spectra and the structural features through the interpretation of the electronic structure. In this review, we list the challenges encountered and propose solutions for dealing with paramagnetic systems with the greatest satisfaction. In our intentions, this is a practical toolkit for optimizing acquisition and processing parameters for routine experiments aimed at detecting signals influenced by the hyperfine interaction. The implications of paramagnetic shift and line broadening are examined. With this endeavor, we wish to encourage non-expert users to consider the application of paramagnetic NMR to their systems. [ABSTRACT FROM AUTHOR]

The suppression of ferroquadrupolar order in TmVO4 in a magnetic field is well-described by the transverse field Ising model, enabling detailed studies of critical dynamics near the quantum phase transition. We describe nuclear magnetic resonance measurements in pure and Y-doped single crystals. The non-Kramers nature of the ground state doublet leads to a unique form of the hyperfine coupling that exclusively probes the transverse field susceptibility. Our results show that this quantity diverges at the critical field, in contrast to the mean-field prediction. Furthermore, we find evidence for quantum critical fluctuations present near Tm-rich regions in Y-doped crystals at levels beyond which long-range order is suppressed, suggesting the presence of quantum Griffiths phases.

Prevalent PET imaging reconstructs 2γ-photon pairs emitted after an annihilation from para-positronium (p-Ps) and rejects 3γ events from ortho-positronium (o-Ps) as noises. The 3γ/2γ decay ratio is ~ 3/7 in human body theoretically but in fact significantly lower due to pick-off process, hence PET imaging quality is well controlled. In a PET-MR hybrid unit, the MR magnetic field alters positronium decay patterns through magnetic quenching: all o-Ps and excited p-Ps states are split into finer quantum states under strong magnetic field, thus transitions between some triplet and singlet finer states (mz = 0) were no longer forbidden, thus some o-Ps converts to p-Ps spontaneously by emitting hyperfine split (HFS) photons, which also drops 3γ/2γ ratio hence helps PET imaging quality. However, inverse magnetic quenching might also occur if any external source of HFS frequencies is nearby, thus many p-Ps convert to o-Ps by absorbing those HFS photons (induced HFS transitions). This will dramatically increase 3γ/2γ ratio and hence degrade PET imaging quality instantaneously. The HFS spectrum lies in a broad range of microwaves, from 0.02 to 200 GHz. To prevent inverse magnetic quenching, it is necessary to block external microwave sources outside the hybrid vault, by adding a thin metal layer at all directions of the vault. This could be achieved by adopting the metallic Faraday Cage, which was originally for MR shielding, with possible amendment if necessary. The frequencies of excitation pulses in MR imaging overlap with HFS spectrum, however, the chance for mutual interference during hybrid imaging is small, hence there seems no need to veto each other during hybrid scans. [ABSTRACT FROM AUTHOR]

Individual electron–nuclear spin systems in solids are promising platforms for implementation of second-generation quantum technologies. The recognized leader among such systems is the negatively charged nitrogen–vacancy color center (NV center) in diamond with hyperfine coupling to nuclear spins of carbon-13 (13C), which are widely used as a quantum memory in emerging quantum technologies because of their weak interaction with the environment. Recently, pairs of 13C–13C nuclei (dimers) in diamond with NV centers have been proposed and actively studied for this purpose because they have extremely long coherence times (minutes at room temperature) in the singlet state. The eigenstates of the spin Hamiltonian of the NV–13C–13C system were found and used to calculate the probabilities of EPR transitions between nuclear-spin sublevels of NV-center states with electron spin projections mS = 0 and mS = –1. The obtained expressions form the basis for choosing the optimal parameters of microwave and radiofrequency pulses transforming a particular dimer into the singlet state. An example of such a prediction for a specific NV–13C–13C spin system using data for the spatial positions of the 13C spins and the internal spin–spin couplings obtained earlier by quantum chemistry methods is presented. [ABSTRACT FROM AUTHOR]

Solid state batteries are becoming more in demand owing to the advancement of EV technology. However, use of liquid electrolytes has become problematic due to their explosive nature. As a result, a lot of research is being done on solid electrolyte-based batteries (also known as "solid state batteries") that employ glasses and alkali metal anodes consisting of Li+, Na+, K+. Herein we demonstrate the influence of V 2 O 5 content on the conductivity characteristics along with their structural and thermal properties of melt-quenched V 2 O 5 -substituted lithium-bismuth-boro-phosphate glasses. The produced glasses were meticulously examined using XRD, FTIR, DTA, 11B-NMR, EPR, and impedance analyzer methods. Structural studies reveal the formation of non-crystalline/amorphous glasses having thermal stability up to 800 °C. Both FTIR and 11B-NMR results reveals the presence of borate groups, i.e., both BO 4 and BO 3. Additionally, EPR results exhibits hyperfine splitting of tetragonal V 2 O 5 , whose distortion varies with the content of V 2 O 5 in the host glass. Furthermore, impedance and dielectric spectroscopy were used to explore the ac and dc conductivities in the frequency and temperature ranges 10 Hz - 3 MHz and 473–623 K respectively. The analyzed results show that both ac and dc conductivities increase with V 2 O 5 content and the conductivity is more ionic in nature. Overall, the investigated results will enhance the fundamental understanding of conducting behaviour of glasses containing alkali and transition metal ions for the development of solid-state batteries. [ABSTRACT FROM AUTHOR]

The copper-containing nitrite reductase from Neisseria gonorrhoeae has been shown to play a critical role in the infection mechanism of this microorganism by producing NO and abolishing epithelial exfoliation. This enzyme is a trimer with a type 1 copper center per subunit and a type 2 copper center in the subunits interface, with the latter being the catalytic site. The two centers were characterized for the first time by EPR and CD spectroscopy, showing that the type 1 copper center has a high rhombicity due to its lower symmetry and more tetragonal structure, while the type 2 copper center has the usual properties, but with a smaller hyperfine coupling constant (A// = 10.5 mT). The thermostability of the enzyme was analyzed by differential scanning calorimetry, which shows a single endothermic transition in the thermogram, with a maximum at 94 °C, while the CD spectra in the visible region indicate the presence of the type 1 copper center up to 80 °C. The reoxidation of the N. gonorrhoeae copper-containing nitrite reductase in the presence of nitrite were analyzed by visible spectroscopy and showed a pH dependence, being higher at pH 5.5–6.0. The high thermostability of this enzyme may be important to maintaining a high activity in the extracellular space and to making it less susceptible to denaturation and proteolysis, contributing to the proliferation of N. gonorrhoeae. [ABSTRACT FROM AUTHOR]

The ongoing experimental efforts to measure the hyperfine transition in muonic hydrogen prompt an accurate evaluation of the proton-structure effects. At the leading order in α , which is O (α 5) in the hyperfine splitting (hfs), these effects are usually evaluated in a data-driven fashion, using the empirical information on the proton electromagnetic form factors and spin structure functions. Here we perform a first calculation based on the baryon chiral perturbation theory (B χ PT). At leading orders it provides a prediction for the proton polarizability effects in hydrogen (H) and muonic hydrogen (μ H). We find large cancellations among the various contributions leading to, within the uncertainties, a zero polarizability effect at leading order in the B χ PT expansion. This result is in significant disagreement with the current data-driven evaluations. The small polarizability effect implies a smaller Zemach radius R Z , if one uses the well-known experimental 1S hfs in H or the 2S hfs in μ H. We, respectively, obtain R Z (H) = 1.010 (9) fm, R Z (μ H) = 1.040 (33) fm. The total proton-structure effect to the hfs at O (α 5) is then consistent with previous evaluations; the discrepancy in the polarizability is compensated by the smaller Zemach radius. Our recommended value for the 1S hfs in μ H is 182.640 (18) meV. [ABSTRACT FROM AUTHOR]

In this study, the superoxide radical O2•− formed by treating Ti(OR)4 (R = iPr, nBu) with H2O2 in the presence of KOH was detected in the EPR spectra. The g-tensor of this radical differs from the typical values reported for a superoxide on various TiO2 surfaces. On the other hand, similar g-tensor components g||(zz = 2.10 ± 0.01, g⊥ = 2.005 ± 0.003 assigned to the O2•− were previously observed for radicals in aqueous solutions in the presence of K2O, alkaline solutions of DMSO, and water/DMSO mixtures. A common factor in all these systems is the presence of alkali ions. However, there was no structural support for the possible interaction of alkali ions with a superoxide in these systems. The use of multifrequency pulsed EPR techniques in this work revealed the stabilization of the O2•− near the K+ ion and its involvement in a strong hydrogen bond with the surface. These findings are consistent with the features previously reported for superoxides on a Na pre-covered MgO surface. Interactions with a closely located 23Na and a strongly coupled 1H proton were also seen in the HYSCORE spectra but assigned to two different superoxides with various gzz values presented in the sample. [ABSTRACT FROM AUTHOR]

We revisit the contributions of order α2(Zα)5m and α2(Zα)EF, respectively, to the Lamb shift and to the hyperfine splitting from mixed self-energy-vacuum-polarization diagrams, involving fermionic loop. We use modern multi-loop calculation techniques based on IBP reduction and differential equations. We construct the ϵ-regular basis [1] and explicitly demonstrate that it is compatible with the renormalization. We obtain analytic results in terms of one-fold integral involving elliptic function and dilogarithm. As a by-product, we obtain the analogous contribution for the limiting cases of heavy and light fermionic loop. [ABSTRACT FROM AUTHOR]

We employ the heavy quark effective theory (HQET) to give spin-parity quantum numbers for the bottom strange states BsJ (6063) and BsJ (6114) recently observed by the LHCb Collaboration [9]. By exploring flavor-independent parameters |$\Delta _{F}^{(c)} =\Delta _{F}^{(b)}$| and |$\lambda _{F}^{(c)} = \lambda _{F}^{(b)}$| appearing in the HQET Lagrangian, we calculate the masses of the experimentally missing bottom strange meson states 2 S , 1 P , 1 D. The parameter Δ F appears in the HQET Lagrangian and gives the spin-averaged mass splitting between excited-state doublets (F) and ground-state doublets (H). Another parameter λ F comes from first-order corrections in the HQET Lagrangian and gives hyperfine splittings. We also analyze these bottom strange masses by taking 1/ mQ corrections, which lead to modifications of parameter terms of |$\Delta _{F}^{(b)} =\Delta _{F}^{(c)} + \delta \Delta _F$| and |$\lambda _{F}^{(b)} = \lambda _{F}^{(c)}\delta \lambda _F$|⁠. Further, we analyze their two-body decays, couplings, and branching ratios via the emission of light pseudoscalar mesons. Based on the predicted masses and decay widths, we tentatively identify the states BsJ (6063) as 23 S 1 and BsJ (6114) as 13 D 1. Our predictions provide crucial information for future experimental studies. [ABSTRACT FROM AUTHOR]

We study the S-wave mass spectra of flavor exotic triply-heavy tetraquark states c c c ¯ q ¯ , c c b ¯ q ¯ , b b c ¯ q ¯ and b b b ¯ q ¯ . We adopt a diquark–antidiquark scheme to solve Schrödinger equation. The calculations are carried out in a nonrelativistic quark model with a color interaction described by a potential computed in AdS/QCD. The AdS/QCD potential model consists of a central potential which reflects short distance and large distance behaviour of QCD, spin dependent term for hyperfine splitting and a constant term. We find stable state candidates in the c c c ¯ q ¯ sector whereas in the c c b ¯ q ¯ , b b c ¯ q ¯ and b b b ¯ q ¯ sectors all the states lie above corresponding S-wave meson-meson thresholds. [ABSTRACT FROM AUTHOR]

The microwave spectra of benzothiazole were measured in the frequency range 2–26.5 GHz using a pulsed molecular jet Fourier transform microwave spectrometer. Hyperfine splittings arising from the quadrupole coupling of the 14N nucleus were fully resolved and analyzed simultaneously with the rotational frequencies. In total, 194 and 92 hyperfine components of the main species and the 34S isotopologue, respectively, were measured and fitted to measurement accuracy using a semi-rigid rotor model supplemented by a Hamiltonian accounting for the 14N nuclear quadrupole coupling effect. Highly accurate rotational constants, centrifugal distortion constants, and 14N nuclear quadrupole coupling constants were deduced. A large number of method and basis set combinations were used to optimize the molecular geometry of benzothiazole, and the calculated rotational constants were compared with the experimentally determined constants in the course of a benchmarking effort. The similar value of the χcc quadrupole coupling constant when compared to other thiazole derivatives indicates only very small changes of the electronic environment at the nitrogen nucleus in these compounds. The small negative inertial defect of −0.056 uÅ2 hints that low-frequency out-of-plane vibrations are present in benzothiazole, similar to the observation for some other planar aromatic molecules. [ABSTRACT FROM AUTHOR]

The influence of magnetic fields on chemical reactions, including biological ones, has been and still is a topical subject in the field of scientific research. Experimentally discovered and theoretically substantiated magnetic and spin effects in chemical radical reactions form the basis of research in the field of spin chemistry. In the present work, the effect of a magnetic field on the rate constant of the bimolecular spin-selective recombination of radicals in the bulk of a solution is considered theoretically for the first time, taking into account the hyperfine interaction of radical spins with their magnetic nuclei. In addition, the paramagnetic relaxation of unpaired spins of the radicals and the non-equality of their g-factors that also influence the recombination process are taken into account. It is found that the reaction rate constant can vary in magnetic field from a few to half a dozen percent, depending on the relative diffusion coefficient of radicals, which is determined by the solution viscosity. It is shown that the consideration of hyperfine interactions gives rise to the presence of resonances in the dependence of the rate constant on the magnetic field. The magnitudes of the magnetic fields of these resonances are determined by the hyperfine coupling constants and difference in the g-factors of the recombining radicals. Analytical expressions for the reaction rate constant of the bulk recombination for magnetic fields larger than hfi (hyperfine interaction) constants are obtained. In general, it is shown for the first time that accounting for hyperfine interactions of radical spins with magnetic nuclei significantly affects the dependence of the reaction rate constant of the bulk radical recombination on the magnetic field. [ABSTRACT FROM AUTHOR]

Identification of the external electromagnetic fields and internal hyperfine parameters which optimize the quantum singlet-triplet yield of simplified radical pairs modeled by Schrödinger system with spin Hamiltonians given by the sum of Zeeman interaction and hyperfine coupling interaction terms are analyzed. A method that combines sensitivity analysis with Tikhonov regularization is implemented. Numerical results demonstrate that the quantum singlet-triplet yield of the radical pair system can be significantly reduced if optimization is pursued simultaneously for both external magnetic fields and internal hyperfine parameters. The results may contribute towards understanding the structure-function relationship of a putative magnetoreceptor to manipulate and enhance quantum coherences at room temperature and leveraging biofidelic function to inspire novel quantum devices. [ABSTRACT FROM AUTHOR]

A test set of N,N,N',N'-tetrasubstituted p-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised "J-style" basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, ω B97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an R 2 value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded. [ABSTRACT FROM AUTHOR]

Two isomeric 2-bromomethylpyridine Cu(II) complexes [Cu(C6H9NBr)2(NO3)2] with 2-bromo-5-methylpyridine (L1) and 2-bromo-4-methylpyridine (L2) were synthesized as air-stable blue materials in good yields. The crystal structures were different with [Cu(L1)2(NO3)2] (CuL1) crystallizing in the monoclinic space group P21/c, while the 4-methyl derivative CuL2 was solved and refined in triclinic P 1 ¯ . The orientation of the Br substituents in the molecular structure (anti (CuL1) vs. syn (CuL2) conformations) and the geometry around Cu(II) in an overall 4 + 2 distorted coordination was very different with two secondary (axially elongated) Cu–O bonds on each side of the CuN2O2 basal plane in CuL1 or both on one side in CuL2. The two Br substituents in CuL2 come quite close to the Cu(II) centers and to each other (Br⋯Br ~3.7 Å). Regardless of these differences, the thermal behavior (TG/DTA) of both materials is very similar with decomposition starting at around 160 °C and CuO as the final product. In contrast to this, FT-IR and Raman frequencies are markedly different for the two isomers and the UV–vis absorption spectra in solution show marked differences in the π–π* absorptions at 263 (CuL2) or 270 (CuL1) nm and in the ligand-to-metal charge transfer bands at around 320 nm which are pronounced for CuL1 with the higher symmetry at the Cu(II) center, but very weak for CuL2. The T-dependent susceptibility measurements also show very similar results (µeff = 1.98 µB for CuL1 and 2.00 µB for CuL2 and very small Curie–Weiss constants of about −1. The EPR spectra of both complexes show axial symmetry, very similar averaged g values of 2.123 and 2.125, respectively, and no hyper-fine splitting. [ABSTRACT FROM AUTHOR]

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 Δ pol. Data-driven evaluations of Δ pol have long been in significant tension with baryon chiral perturbation theory. Here we present improved results for Δ pol driven by new spin structure data, reducing the long-standing tension between theory and experiment and halving the dominating uncertainty in hyperfine splitting calculations. [ABSTRACT FROM AUTHOR]

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

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

Nuclear Magnetic Resonance (NMR) spectroscopy is the ideal tool to address the structure, reactivity and dynamics of both inorganic and biological substances. The knowledge of nuclear spin interaction and spin dynamics is increasingly consolidated, and this allows for tailoring pulse sequences. When dealing with paramagnetic systems, several decades of research have led to the development of rule-of-the-thumb criteria for optimizing the experiments, allowing for the detection of nuclei that are in very close proximity to the metal center. In turn, the observation of these systems, coupled with the development of robust and accessible quantum chemical methods, is promising to provide a link between the spectra and the structural features through the interpretation of the electronic structure. In this review, we list the challenges encountered and propose solutions for dealing with paramagnetic systems with the greatest satisfaction. In our intentions, this is a practical toolkit for optimizing acquisition and processing parameters for routine experiments aimed at detecting signals influenced by the hyperfine interaction. The implications of paramagnetic shift and line broadening are examined. With this endeavor, we wish to encourage non-expert users to consider the application of paramagnetic NMR to their systems.

Breast cancer is one of the major types of cancer around the world, and early diagnosis is essential for successful treatment. New contrast agents (CAs), with reduced toxicology, are needed to improve diagnosis. One of the most promising Magnetic Resonance Imaging (MRI) CA is based on rhenium conjugated with a benzothiazole derivate (ReABT). In this sense, DFT has been used to evaluate the best methodology for calculating the hyperfine coupling constant (Aiso) of ReABT. Then, a thermodynamic analysis was performed to confirm the stability of the complex. Furthermore, a docking study of ReABT at the enzyme PI3K active site and Aiso calculations of ReABT in the enzyme environment were carried out. The best methodology for the Aiso calculation of ReABT was using the M06L functional, SARC-ZORA-TZVP (for Re) and TZVP (for all other atoms) basis set, relativistic Hamiltonian, and the CPCM solvation model with water as the solvent which confirm that the relativistic effects are important for calculating the Aiso values. In addition, thermodynamic analysis indicates that ReABT presents a higher stability and a lower toxicity than Gd-based CAs. The docking studies point out that ReABT interacts with amino acids residues of alanine, aspartate, and lysine from the PI3K active site. Considering the enzyme environment, Aiso values decrease significantly. These findings indicate that the CA candidate ReABT could be a good candidate for a new contrast agent. [ABSTRACT FROM AUTHOR]

Muons are puzzling physicists since their discovery when they were first thought to be the meson predicted by Yukawa to mediate the strong force. The recent result at Fermilab on the muon g-2 anomaly puts the muonic sector once more under the spotlight and calls for further measurements with this particle. Here, we present the results of the measurement of the 2S1/2, F = 0 → 2P1/2, F = 1 transition in Muonium. The measured value of 580.6(6.8) MHz is in agreement with the theoretical calculations. A value of the Lamb shift of 1045.5(6.8) MHz is extracted, compatible with previous experiments. We also determine the 2S hyperfine splitting in Muonium to be 559.6(7.2) MHz. The measured transition being isolated from the other hyperfine levels holds the promise to provide an improved determination of the Muonium Lamb shift at a level where bound state QED recoil corrections not accessible in hydrogen could be tested. This result would be sensitive to new physics in the muonic sector, e.g., to new bosons which might provide an explanation of the g-2 muon anomaly and allow to test Lorentz and CPT violation. We also present the observation of Muonium in the n = 3 excited state opening up the possibility of additional precise microwave measurements. Muonium is a hydrogen like bound system with a positive muon and an electron. Here the authors measure the Lamb shift and frequency of the transition from 2S1/2, F = 0 state to 2P1/2, F = 1 state in muonium atom and the hyperfine structure of the 2S level. [ABSTRACT FROM AUTHOR]

Negative ions are important in many areas of science and technology, e.g., in interstellar chemistry, for accelerator-based radionuclide dating, and in anti-matter research. They are unique quantum systems where electron-correlation effects govern their properties. Atomic anions are loosely bound systems, which with very few exceptions lack optically allowed transitions. This limits prospects for high-resolution spectroscopy, and related negative-ion detection methods. Here, we present a method to measure negative ion binding energies with an order of magnitude higher precision than what has been possible before. By laser-manipulation of quantum-state populations, we are able to strongly reduce the background from photodetachment of excited states using a cryogenic electrostatic ion-beam storage ring where keV ion beams can circulate for up to hours. The method is applicable to negative ions in general and here we report an electron affinity of 1.461 112 972(87) eV for 16O. High-precision measurements are useful to find isotopic shifts and electron correlation. Here the authors measure electron affinity and hyperfine splitting of atomic oxygen with higher precision than previous studies. [ABSTRACT FROM AUTHOR]

We examine the properties of ditauonium, an exotic atom consisting of a pair of opposite-sign τ leptons bound together by the quantum electrodynamics (QED) interaction in a hydrogen-like state. The energy levels, decay modes and associated partial widths, as well as total widths and lifetimes of the ortho- and para-ditauonium states are calculated. Higher-order QED effects – including Lamb shifts, hyperfine splitting structure, and partial decay widths corrections – are incorporated up to approximately next-to-next-to-leading-order (NNLO) accuracy. Beyond the dominant diphoton and difermion decays, the rates of rare decay channels – including Dalitz, radiative, triple-photon, double-Dalitz, four-fermion, and neutrinos final states – are determined. [ABSTRACT FROM AUTHOR]

The zero-point energies (ZPEs) of paramagnetic molecules, free and compressed in a C59N paramagnetic cage, were computed. The excess of energy acquired by molecules under compression depended on the deuterium and tritium isotopes which ranged from 6–8 kcal/mol for H2+ to 1.0–1.5 kcal/mol for HO• and HO2. The differences in the ZPEs of compressed isotopic molecules resulted in large deuterium and tritium isotope effects which differed for singlet and triplet spin states. The hyperfine coupling (HFC) constants for protons and 17O nuclei decreased under compression, confirming the leakage of the unpaired π-electron from the central oxygen atom of guest molecules into the system of π-electrons of the cage, and its distribution over 60 atoms of the C59N. The latter seems to be the reason why the nitrogen-14 HFCs for C59N remain almost unchanged upon encapsulation of guest molecules. The singlet-triplet splitting is shown to depend on the Coulomb interaction, which controls the sign of the exchange potential. The importance of compression effects on the functioning of enzymes as molecular compressing devices is discussed. [ABSTRACT FROM AUTHOR]

Concentration variation of Mn2+ ions doped zincaluminoborophosphate (ZnAlBP) glasses of 40 ZnO + 25 H3BO3 + (30-x) P2O5 + 5 Al2O3 + x MnO with 0 ≤ x ≤ 0.8 (x=0, 0.2, 0.4, 0.6 and 0.8) have been prepared and investigated by structural and spectroscopic techniques. The XRD diffractograms confirm the amorphous nature of the prepared samples. The FTIR spectra reveal the existence of BO3 and BO4 units along with fundamental P-O-H and B-O-H structural units in the present glass system. The Optical absorption spectra exhibit two low intensity bands centered at 407 nm (24,570 cm-1) and 689 (14,514 cm-1). These bands were assigned to 6A1g(S) → 4A1g (G) + 4Eg (G) and6A1g(S) → 4T1g (G) characteristic transitions of Mn2+ ions in octahedral symmetry. Tauc's plots were drawn to measure the optical band gaps for the direct and indirect transitions. The energy gaps show a decreasing trend for the selected ZnAlBP: Mn2+ glass system. The well-resolved hyperfine splitting EPR spectra of prepared glass samples exhibit resonance at g ≈ 1.98 indicating the Mn2+ ions are in octahedral site symmetry. The hyperfine splitting factor (hfs), the number of spin levels (N), hyperfine constant (A), zero-field splitting parameter (D), and paramagnetic susceptibility (χ) have been determined. The magnitude of g indicates the predominant ionicity in the glasses. [ABSTRACT FROM AUTHOR]

In this study, the superoxide radical O2•− formed by treating Ti(OR)4 (R = iPr, nBu) with H2O2 in the presence of KOH was detected in the EPR spectra. The g-tensor of this radical differs from the typical values reported for a superoxide on various TiO2 surfaces. On the other hand, similar g-tensor components g||(zz = 2.10 ± 0.01, g⊥ = 2.005 ± 0.003 assigned to the O2•− were previously observed for radicals in aqueous solutions in the presence of K2O, alkaline solutions of DMSO, and water/DMSO mixtures. A common factor in all these systems is the presence of alkali ions. However, there was no structural support for the possible interaction of alkali ions with a superoxide in these systems. The use of multifrequency pulsed EPR techniques in this work revealed the stabilization of the O2•− near the K+ ion and its involvement in a strong hydrogen bond with the surface. These findings are consistent with the features previously reported for superoxides on a Na pre-covered MgO surface. Interactions with a closely located 23Na and a strongly coupled 1H proton were also seen in the HYSCORE spectra but assigned to two different superoxides with various gzz values presented in the sample.

[Display omitted] • The rotational spectrum of 1,1-dichloro-1-silacyclohex-2-ene is reported for the first time. • The hyperfine splitting has been adequately deconvoluted, allowing for meaningful analysis of the quadrupole coupling. • The determined structural parameter values correspond well to other chlorinated silanes. The ground state rotational spectrum of 1,1-dichloro-1-silacyclohex-2-ene has been recorded using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer. Several isotopologues in their natural abundances have been observed in the free-jet expansion, and their spectra assigned, making it possible to present a partial heavy-atom substitution structure. Furthermore, the high resolution of this technique allows the complicated hyperfine splitting pattern to be largely deconvoluted. As a result, the on-diagonal nuclear quadrupole coupling constants for the two chlorine atoms have been determined for all observed isotopologues. Additionally, χ bc is determined for both chlorine atoms of the parent species. The quadrupole coupling tensors for the parent species have been diagonalised, noting some assumptions have been made pertaining to the off-diagonal nuclear quadrupole coupling constants in the principal axis system, to yield reasonable values of χ zz and η which are then compared. [ABSTRACT FROM AUTHOR]

Obtaining an accurate first-principle description of the electronic properties of dopant qubits is critical for engineering and optimizing high-performance quantum computing. However, density functional theory (DFT) has had limited success in providing a full quantitative description of these dopants due to their large wavefunction extent. Here, we build on recent advances in DFT to evaluate phosphorus dopants in silicon on a lattice comprised of 4096 atoms with hybrid functionals on a pseudopotential and all-electron mixed approach. Remarkable agreement is achieved with experimental measurements including: the electron-nuclear hyperfine coupling (115.5 MHz) and its electric field response (−2.65 × 10−3 μm2/V2), the binding energy (46.07 meV), excited valley-orbital energies of 1sT2 (37.22 meV) and 1sE (35.87 meV) states, and super-hyperfine couplings of the proximal shells of the silicon lattice. This quantitative description of spin and orbital properties of phosphorus dopant simultaneously from a single theoretical framework will help as a predictive tool for the design of qubits. Modelling the quantum transport properties of qubit arrays and the electronic properties of dopant qubits is computationally challenging yet crucial for device optimization in quantum computing. Here, the authors compare different DFT-based methods to describe the properties of shallow donor-based qubits in silicon. [ABSTRACT FROM AUTHOR]

The relaxation time of a single-electron spin is an important parameter for solid-state spin qubits, as it directly limits the lifetime of the encoded information. Thanks to the low spin-orbit interaction and low hyperfine coupling, graphene and bilayer graphene (BLG) have long been considered promising platforms for spin qubits. Only recently, it has become possible to control single-electrons in BLG quantum dots (QDs) and to understand their spin-valley texture, while the relaxation dynamics have remained mostly unexplored. Here, we report spin relaxation times (T1) of single-electron states in BLG QDs. Using pulsed-gate spectroscopy, we extract relaxation times exceeding 200 μs at a magnetic field of 1.9 T. The T1 values show a strong dependence on the spin splitting, promising even longer T1 at lower magnetic fields, where our measurements are limited by the signal-to-noise ratio. The relaxation times are more than two orders of magnitude larger than those previously reported for carbon-based QDs, suggesting that graphene is a potentially promising host material for scalable spin qubits. Graphene has long been considered to be a promising host for spin qubits, however a demonstration of long spin relaxation times for a potential qubit has been lacking. Here, the authors report the electrical measurement of the single-electron spin relaxation time exceeding 200 μs in a bilayer graphene quantum dot. [ABSTRACT FROM AUTHOR]

Precision atomic spectroscopy provides a solid model independent bound on the existence of new dark forces among the atomic constituents. We focus on the keV-GeV region investigating the sensitivity to such dark sectors of the recent measurements on muonic atoms at PSI. To this end we develop for the first time, the effective field theory that describes the leading effect of a new (pseudo-)vector or a (pseudo-)scalar particle of any mass at atomic energies. We identify in the Lamb Shift measurement in muonic deuterium (μD) and the 2s Hyperfine Splitting (HFS) in muonic hydrogen (μH) the most promising measurements to probe respectively spin-independent and spin-dependent new forces. Furthermore, we evaluate the expression of the vector force HFS finding that a future measurement of the 2s HFS in regular hydrogen could provide the strongest atomic bound for such a force for masses above 100 MeV. [ABSTRACT FROM AUTHOR]

Atomically thin two-dimensional (2D) materials are ideal host systems for quantum defects as they offer easier characterisation, manipulation and read-out of defect states as compared to bulk defects. Here we introduce the Quantum Point Defect (QPOD) database with more than 1900 defect systems comprising various charge states of 503 intrinsic point defects (vacancies and antisites) in 82 different 2D semiconductors and insulators. The Atomic Simulation Recipes (ASR) workflow framework was used to perform density functional theory (DFT) calculations of defect formation energies, charge transition levels, Fermi level positions, equilibrium defect and carrier concentrations, transition dipole moments, hyperfine coupling, and zero-field splitting. Excited states and photoluminescence spectra were calculated for selected high-spin defects. In this paper we describe the calculations and workflow behind the QPOD database, present an overview of its content, and discuss some general trends and correlations in the data. We analyse the degree of defect tolerance as well as intrinsic dopability of the host materials and identify promising defects for quantum technological applications. The database is freely available and can be browsed via a web-app interlinked with the Computational 2D Materials Database (C2DB). [ABSTRACT FROM AUTHOR]

Ultralight scalar fields such as axions can form clouds around rotating black holes (BHs) by the superradiant instability. It is important to consider the evolution of clouds associated with BH binaries for the detectability of the presence of clouds through gravitational wave signals and observations of the mass and spin parameters of BHs. The impact on the axion cloud due to the tidal perturbation from the companion in a binary system was first studied in D. Baumann et al. Phys. Rev. D, 101 , 083019. Here, we re-examine this issue taking into account the following points. First, we study the influence of higher-multipole moments. Second, we consider the backreaction due to the angular momentum transfer between the cloud and the orbital motion. This angular momentum transfer further causes the backreaction to the hyperfine split through the change in geometry. Finally, we calculate the particle number flux to infinity induced by the tidal interaction. As a result, we find that the scalar field is not reabsorbed by the BH. Instead, the scalar particles are radiated away to evaporate during the inspiral, irrespective of the direction of the orbital motion, for almost equal mass binaries. [ABSTRACT FROM AUTHOR]

Pyrrolidine nitroxides with four bulky alkyl substituents adjacent to N–O group are known for their high resistance to bioreduction. The 3,4-unsubstituted 2-tert-butyl-2-ethylpyrrolidine-1-oxyls were prepared from the corresponding 2-tert-butyl-1-pyrroline-1-oxides via either the addition of ethinylmagnesium bromide with subsequent hydrogenation or via treatment with ethyllithium. The new nitroxides showed excellent stability to reduction with ascorbate with no evidence for additional large hyperfine couplings in the EPR spectra. [ABSTRACT FROM AUTHOR]

We revisit the recipe for hadron formation in the Lund string hadronization model. Given an incoming quark or quark-diquark pair, weights for hadron formation are updated to take hyperfine splitting effects arising from the mass difference between u , d -type and s -type quarks. We find that the procedure improves the description of hadron yields in e + e - collisions and the ϕ cross section in neutral current DIS. We also show results for proton collisions, and discuss the future use of this study in the context of small system collectivity. [ABSTRACT FROM AUTHOR]

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 g values of a paramagnetic center and hyperfine splitting (A) caused by its interaction with neighboring magnetic nuclei in a molecule provide important structural and electronic information. However, in the presence of g- and/or A-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 g and A 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 g 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 g and hyperfine coupling constant values, and revealed features that were buried in the overlapped spectra. [ABSTRACT FROM AUTHOR]

In this study, the EPR hyperfine coupling constants and spin densities of cation and anion radicals of triafulvalene, pentafulvalene and heptafulvalene were calculated by using DFT method with B3LYP functional at LanL2DZ level. The hyperfine structures formed EPR spectra of all the cation and anion radicals were determined. It was seen that in the cation cases of triafulvalene and heptafulvalene spin density is delocalized throughout the molecule whereas in their anion cases it is essentially localized on only a single ring. The reason of this distribution of the unpaired spin was investigated by their Natural Bond Orbital (NBO) and Mullikan charge analyses. These analyses showed that in the anion cases of the molecules the interaction energies between the interring C-C bond and the ring C-C bonds are different for both the two rings and one of them is quite higher than the other. The simulated EPR spectra obtained by EPR Simulator software program were harmoniously given with together their experimental spectra. [ABSTRACT FROM AUTHOR]