Resolved Hyperfine Research Articles

A comparison of pulse and CW EPR [formula omitted]-relaxation measurements of an inhomogeneously broadened nitroxide spin probe undergoing Heisenberg spin exchange 2. The intercept discrepancy

Experimental confirmation of a theoretical prediction of a non-linear broadening of the spin packets of nitroxide free radicals due to Heisenberg spin exchange at low concentrations, C, is presented. A recent demonstration that spectra with resolved proton hyperfine structure may be analyzed efficiently and accurately was utilized to confirm the theory. As C→0, a plot of the spin-packet line width (SPW) curves downward due to the presence of proton hyperfine couplings that increase the number of distinguishable quantum spin states. At higher C, the broadening is linear with C and the results for the spin exchange rate constant determined from the slope of the broadening of the average spin-packet line width and electron spin echo measurements are in agreement. It is shown that applying modest digital smoothing does not change the values of the SPW. An example of a practical application of these methods to published work is presented, allowing an enigma to be resolved.

Spin Crossover and Fluorine-Specific Interactions in Metal Complexes of Terpyridines with Polyfluorocarbon Tails.

In coordination chemistry and materials science, terpyridine ligands are of great interest, due to their ability to form stable complexes with a broad range of transition metal ions. We report three terpyridine ligands containing different perfluorocarbon (PFC) tails on the backbone and the corresponding FeII and CoII complexes. The CoII complexes display spin crossover close to ambient temperature, and the nature of this spin transition is influenced by the length of the PFC tail on the ligand backbone. The electrochemical properties of the metal complexes were investigated with cyclic voltammetry revealing one oxidation and several reduction processes. The fluorine-specific interactions were investigated by EPR measurements. Analysis of the EPR spectra of the complexes as microcrystalline powders and in solution reveals exchange-narrowed spectra without resolved hyperfine splittings arising from the 59 Co nucleus; this suggests complex aggregation in solution mediated by interactions of the PFC tails. Interestingly, addition of perfluoro-octanol in different ratios to the acetonitrile solution of the sample resulted in the disruption of the F F interactions of the tails. To the best of our knowledge, this is the first investigation of fluorine-specific interactions in metal complexes through EPR spectroscopy, as exemplified by exchange narrowing.

Observation of an Inner-Shell Orbital Clock Transition in Neutral Ytterbium Atoms.

We observe a weakly allowed optical transition of atomic ytterbium from the ground state to the metastable state 4f^{13}5d6s^{2} (J=2) for all five bosonic and two fermionic isotopes with resolved Zeeman and hyperfine structures. This inner-shell orbital transition has been proposed as a new frequency standard as well as a quantum sensor for new physics. We find magic wavelengths through the measurement of the scalar and tensor polarizabilities and reveal that the measured trap lifetime in a three-dimensional optical lattice is 1.9(1)s, which is crucial for precision measurements. We also determine the g factor by an interleaved measurement, consistent with our relativistic atomic calculation. This work opens the possibility of an optical lattice clock with improved stability and accuracy as well as novel approaches for physics beyond the standard model.

Electric Dipole Moments from Stark Effect in Supersonic Expansion: n-Propanol, n-Butanol, and n-Butyl Cyanide.

The orientation and magnitude of the molecular electric dipole moment are key properties relevant to topics ranging from the nature of intermolecular interactions to the quantitative analysis of complex gas-phase mixtures, such as chemistry in astrophysical environments. Stark effect measurements on rotational spectra have been the method of choice for isolated molecules but have become less common with the practical disappearance of Stark modulation spectrometers. Their role has been taken over by supersonic expansion measurements within a Fabry-Perot resonator cavity, which introduces specific technical problems that need to be overcome. Several of the adopted solutions are described and compared. Presently, we report precise electric dipole moment determinations for the two most stable conformers of the selected molecules of confirmed or potential astrophysical relevance: n-propanol, n-butanol, and n-butyl cyanide. All dipole moment components have been precisely determined at supersonic expansion conditions by employing specially designed Stark electrodes and a computer program for fitting the measured Stark shifts, inclusive of cases with resolved nuclear quadrupole hyperfine structure. The experimental values are compared with suitable quantum chemistry computations. It is found that, among the tested levels of computation, vibrationally averaged dipole moments are the closest to the observation and the molecular values are, as in the lighter molecules in the series, largely determined by the hydroxyl or nitrile groups.

A new 13C trityl-based spin label enables the use of DEER for distance measurements

Triarylmethyl (TAM)-based labels, while still underutilized, are a powerful class of labels for pulsed-Electron Spin Resonance (ESR) distance measurements. They feature slow relaxation rates for long-lasting signals, high stability for cellular experiments, and narrow spectral features for efficient excitation of the spins. However, the typical narrow line shape limits the available distance measurements to only single-frequency experiments, such as Double Quantum Coherence (DQC) and Relaxation Induced Dipolar Modulation Enhancement (RIDME), which can be complicated to perform or hard to process. Therefore, widespread usage of TAM labels can be enhanced by the use of Double Electron-Electron Resonance (DEER) distance measurements. In this work, we developed a new spin label, 13C1-mOX063-d24, with a 13C isotope as the radical center. Due to the resolved hyperfine splitting, the spectrum is sufficiently broadened to permit DEER-based experiments at Q-band spectrometers. Additionally, this new label can be incorporated orthogonally with Cu(II)-based protein label. The orthogonal labeling scheme enables DEER distance measurement at X-band frequencies. Overall, the new trityl label allows for DEER-based distance measurements that complement existing TAM-label DQC and RIDME experiments.

Observation of the hyperfine structure and anticrossings of hyperfine levels in the luminescence spectra of LiYF4:Ho3+

Resolved hyperfine structure and narrow inhomogeneously broadened lines in the optical spectra of a rare-earth-doped crystal are favorable for the implementation of various sensors. Here, a well-resolved hyperfine structure in the photoluminescence spectra of LiYF4:Ho single crystals and the anticrossings of hyperfine levels in a magnetic field are demonstrated using a self-made setup based on a Bruker 125HR high-resolution Fourier spectrometer. This is the first observation of the resolved hyperfine structure and anticrossing hyperfine levels in the luminescence spectra of a crystal. The narrowest spectral linewidth is only 0.0022 cm−1. This fact together with a large value of the magnetic g factor of several crystal-field states creates prerequisites for developing magnetic field sensors, which can be in demand in modern quantum information technology devices operating at low temperatures. Very small random lattice strains characterizing the quality of a crystal can be detected using anticrossing points.

Nuclear magnetic resonance of Li8 ions implanted in ZnO

We report on the stability and magnetic state of ion implanted $^{8}\mathrm{Li}$ in single crystals of the semiconductor ZnO using $\ensuremath{\beta}$-detected nuclear magnetic resonance. At ultradilute concentrations, the spectra reveal distinct Li sites from 7.6 to 400 K. Ionized shallow donor interstitial Li is stable across the entire temperature range, confirming its ability to self-compensate the acceptor character of its (Zn) substitutional counterpart. Above 300 K, spin-lattice relaxation indicates the onset of correlated local motion of interacting defects, and the spectra show a site change transition from disordered configurations to substitutional. Like the interstitial, the substitutional shows no resolved hyperfine splitting, indicating it is also fully ionized above 210 K. The electric field gradient at the interstitial $^{8}\mathrm{Li}$ exhibits substantial temperature dependence with a power law typical of noncubic metals.

Collisional excitation of isotopologues of carbon monoxide by molecular hydrogen

ABSTRACTRate coefficients for transitions between the 14 lowest rotational levels, having energies less than 500 K, of the most abundant isotopologue of carbon monoxide,12C16O, caused by collisions with para-H2 and ortho-H2 are reported for temperatures between 5 and 400 K. These data were computed through time-independent close-coupled scattering calculations employing the high-quality potential energy surface (PES) recently calculated by Faure et al. Rate coefficients for collision-induced transitions are required for radiative transfer modelling of molecules present in interstellar clouds under non-equilibrium conditions. In addition, rate coefficients were computed for other carbon monoxide isotopologues, 13C16O, 12C17O, and 12C18O. The PESs for these systems were obtained by transforming the PES for 12C16O–H2 PES. The rotational transitions of 12C17O isotopologue often display resolved hyperfine structure in astronomical spectra. Rate coefficients for collision-induced transitions between the rotational–hyperfine levels of this isotopologue have been computed by the recoupling technique. A simple radiative transfer calculation was performed to illustrate the utility of using such an approach to relate observed intensities in astronomical spectra with molecular abundances.

From Molecular to Cluster Properties: Rotational Spectroscopy of 2-Aminopyridine and of Its Biomimetic Cluster with Water

We report the observation and analysis of the rotational spectrum of a 1:1 cluster between 2-aminopyridine and water (AMW) carried out with supersonic expansion Fourier transform microwave spectroscopy at 4.7–16.5 GHz. Measurements of the 2-aminopyridine monomer (AMP) were also extended up to 333 GHz for the room-temperature rotational spectrum and to resolved hyperfine splitting resulting from the presence of two 14N quadrupolar nuclei. Supersonic expansion measurements for both AMP and AMW were also carried out for two synthesized isotopic species with single deuteration on the phenyl ring. Nuclear quadrupole hyperfine structure has also been resolved for AMW and the derived splitting constants were used as an aid in structural analysis. The structure of the AMW cluster was determined from the three sets of available rotational constants and the hydrogen bonding configuration is compared with those for clusters with water of similarly sized single-ring molecules. Experimental results aided by quantum chemistry computations allow the conclusion that the water molecule is unusually strongly bound by two hydrogen bonds, OH...N and O...HN, to the NCNH atomic chain of AMP with the potential to replace hydrogen bonds to the identical structural segment in cytosine and adenine in CT and AT nucleic acid base pairs.

Wide-band EPR spectroscopy and relaxation study of Tm3+ ions in PbGa2S4 crystal

The PbGa2S4: Tm3+ crystal was investigated by tunable high-frequency EPR spectroscopy. Two thulium centers located in positions with different local symmetry were observed in the frequency range of 9.8–170 GHz. Both spectra with the resolved hyperfine structure correspond to the transition between sublevels of the main quasi-doublet Tm3+ with crystal field splitting of 6.93 GHz and 1.42 GHz. The times of phase memory and spin-lattice relaxation of thulium ions were measured by the spin-echo method for various values of the magnetic field.

Electron nuclear interactions in spin-3/2 color centers in silicon carbide: A high-field pulse EPR and ENDOR study

High-frequency pulsed electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) were used to determine electron nuclear interactions on remote ligand shells of silicon and carbon in spin-3/2 color centers with an optically induced high-temperature spin alignment in hexagonal $4H$-, $6H$-, and rhombic $15R$-silicon carbide (SiC) polytypes. The EPR and ENDOR experimental data relate unambiguously to spin-3/2 centers in which the optically induced alignment of the spin-level populations occurs. The identification is based on resolved ligand hyperfine interactions with carbon and silicon nearest, next-nearest, and the more distant neighbors and on the determination of the unpaired electron spin densities. The hyperfine interactions with $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei are unambiguously separated due to the selective population of the fine-structure levels with certain values of ${\mathrm{M}}_{\mathrm{S}}$. The signs of these interactions and, as a result, the signs of oscillating spin density at $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei, are determined. On the basis of the EPR and optically induced ENDOR measurements, signs of the fine-structure splitting for all the centers were demonstrated, which made it possible to establish the character of optically induced spin alignment, including the inverse populations of the spin levels for these centers. The values of hyperfine interaction with $^{29}\mathrm{Si}$ and $^{13}\mathrm{C}$ nuclei, including those remote from the localization of the spin-3/2 center, are tabulated, which can be used by a number of algorithms in quantum information processing as long-term memory.

Initialization protocol for efficient quantum memories using resolved hyperfine structure

We describe a quantum memory spectral preparation strategy that maximises memory efficiency and bandwidth in materials such as 167 Er3+:Y2SiO5 in a high field regime, where the hyperfine structure is resolved. We demonstrate the method in 167 Er3+:Y2SiO5 by preparing spectrally isolated 18 dB-absorbing features on a < 1 dB background. Using these features we create an atomic frequency comb and show quantum storage of 200 ns pulses with 22% efficiency, limited by the background absorption which arises from laser instability. We describe the experimental improvements needed to reach the material limits: O(1) s spin state storage, O(100) MHz bandwidth, and > 90% efficiency.

Rotational spectroscopic study and astronomical search for propiolamide in Sgr B2(N).

For all the amides detected in the interstellar medium (ISM), the corresponding nitriles or isonitriles have also been detected in the ISM, some of which have relatively high abundances. Among the abundant nitriles for which the corresponding amide has not yet been detected is cyanoacetylene (HCCCN), whose amide counterpart is propiolamide (HCCC(O)NH2). With the aim of supporting searches for this amide in the ISM, we provide a complete rotational study of propiolamide from 6 GHz to 440 GHz. Time-domain Fourier transform microwave (FTMW) spectroscopy under supersonic expansion conditions between 6 GHz and 18 GHz was used to accurately measure and analyze ground-state rotational transitions with resolved hyperfine structure arising from nuclear quadrupole coupling interactions of the 14N nucleus. We combined this technique with the frequency-domain room-temperature millimeter wave and submillimeter wave spectroscopies from 75 GHz to 440 GHz in order to record and assign the rotational spectra in the ground state and in the low-lying excited vibrational states. We used the ReMoCA spectral line survey performed with the Atacama Large Millimeter/submillimeter Array toward the star-forming region Sgr B2(N) to search for propiolamide. We identified and measured more than 5500 distinct frequency lines of propiolamide in the laboratory. These lines were fitted using an effective semi-rigid rotor Hamiltonian with nuclear quadrupole coupling interactions taken into consideration. We obtained accurate sets of spectroscopic parameters for the ground state and the three low-lying excited vibrational states. We report the nondetection of propiolamide toward the hot cores Sgr B2(N1S) and Sgr B2(N2). We find that propiolamide is at least 50 and 13 times less abundant than acetamide in Sgr B2(N1S) and Sgr B2(N2), respectively, indicating that the abundance difference between both amides is more pronounced by at least a factor of 8 and 2, respectively, than for their corresponding nitriles. Although propiolamide has yet to be included in astrochemical modeling networks, the observed upper limit to the ratio of propiolamide to acetamide seems consistent with the ratios of related species as determined from past simulations. The comprehensive spectroscopic data presented in this paper will aid future astronomical searches.

Insight on Ni(II) and Cu(II) complexes of biguanide derivatives developed as effective antimicrobial and antitumour agents

Six compounds of the types [M(dmbg)2]·nH2O ((1) M: Ni, n = 0; (4) M: Cu, n = 1; Hdmbg: N,N′‐dimethylbiguanide) and, respectively, [ML]·nH2O (where (2) M: Ni, L: L1, n = 0; (3) M: Ni, L: L2, n = 0; (5) M: Cu, L: L1, n = 0 and (6) M: Cu, L: L2, n = 3, H2L1: ligand resulted from the condensation of (1) with ammonia and formaldehyde and H2L2: ligand resulted from the condensation of (4) with hydrazine and formaldehyde) were characterized as mononuclear species through information provided by NMR, electronic paramagnetic resonance (EPR) and UV–Vis spectroscopy as well as cyclic voltammetry. All data are consistent with macrocyclic formation by condensation. The complexes adopt a distorted square planar geometry resulting from the chelating behaviour of the corresponding ligands. The EPR spectra recorded after the addition of Cu(II) complexes into the corresponding Ni(II) complexes show a well resolved hyperfine structure with the superhyperfine pattern corresponding to four nitrogen atom donors. The cathodically shift of Epc2 for both series can be correlated with the increased stability of the M(I) species through macrocyclic ligands. Geometry optimization studies for complexes (2), (3), (5) and (6) have further confirmed the experimental data. The pharmacokinetic computational results indicate that the complexes exhibit medium to low intestinal absorption and slow blood–brain barrier permeability but low toxicity. Their predictive pharmacodynamic profiles show that the compounds present the ability to inhibit protease activity. By corroborating the results of the in silico analysis with the experimental ones, the most promising complexes for antimicrobial applications are (1) and (2) and, respectively, (4) and (6) for the development of novel antitumour strategies.

Novel VO (IV) complexes derived from a macrochelates: Synthesis, characterization, molecular modeling and in vivo insulin‐mimic activity studies

For the development of extensive investigations into a potential medicinal application of vanadium coordination compounds for the oral treatment of diabetes, new mono and bimetallic VO (IV) complexes with N,N′‐(2,2′‐(9,10‐dihydro‐9,10‐ethanoanthracene‐11,12‐dicarbonyl) bis (hydrazine‐1‐carbonothioyl)) dibenzamide (H6EBT) and 2,2′‐((9S,10S,11R,12R)‐9,10‐dihydro‐9,10‐ethanoanthracene‐11, 12‐dicarbonyl) bis (N‐phenylhydrazine‐1‐carboxamide) (H6EPH) have been isolated and characterized. The FTIR and NMR spectral data revealed that H6EBT acts as neutral tridentate and dibasic hexadentate while H6EPH as dibasic tridentate and tetrabasic hexadentate. The electronic and ESR spectra indicated that complexes has octahedral geometry. ESR spectrum of [(VO)(H6EBT)(SO4)].5H2O gives a well resolved hyperfine eight‐line pattern typical spectrum for mononuclear vanadyl complexes with g˃ g⊥ = 1.9 suggesting that the ligand donor atoms ONS are coplanar with the two chelate rings forming octahedral geometry. Also, the high parallel hyperfine splitting value, A = 0.0108, than perpendicular one (A⊥ = 0.0087) indicated that the single d‐ electron is in a σ‐nonbonding orbital and aiming away from the equatorial ligands. On the other hand, the EPR spectra of the binuclear [(VO)2(H4EBT)(SO4)]3H2O and [(VO)2(H2EPH)(H2O)2].10H2O complexes gave a single broad line centered at g = 2.05 and 2.07, respectively, without resolved hyperfine structure paramagnetic triplet (S = 1) is consistent with the anomalous value of the magnetic moment value (μeff = 1.100 and 0.99 B.M.) supporting a binuclear nature. The TG analyses confirmed the existence of solvent molecules inside and/or outside the coordination sphere. The DFT molecular modeling of ligands and its VO (IV) complexes supported the suggested geometries. Also, all compounds were screened for in vivo insulin‐mimetic activity.

The electronic spectrum of the jet-cooled stibino (SbH2) free radical.

The Ã2A1-X̃2B1 electronic transition of the jet-cooled stibino (SbH2 and SbD2) free radical has been observed for the first time using laser induced fluorescence (LIF) detection. The radicals were produced by a pulsed electric discharge through a mixture of stibine (SbH3 or SbD3) in high pressure argon at the exit of a pulsed molecular beam valve. SbH2 exhibits only three LIF bands, assigned as 21 0, 00 0, and 20 1, with a fluorescence lifetime (τ), which decreases from ∼50 ns for 00 to <10 ns for 21. LIF transitions to the 00 (τ ∼ 2 µs), 21 (τ ∼ 400 ns), and 22 (τ ∼ 75 ns) upper vibronic states of SbD2 were also observed. High-resolution spectra exhibited large spin-rotation splittings and small resolved antimony hyperfine splittings due to a substantial Fermi contact interaction in the excited state. The experimentally determined rotational constants gave effective molecular structures of r0 ″ = 1.724(2) Å, θ0 ″ = 90.38(7)° and r0 ' = 1.693(6) Å, θ0 ' = 120.6(3)°. The ground state bending vibrational levels up to eight quanta (6404 cm-1) in SbH2 and 12 quanta (6853 cm-1) in SbD2 were measured from dispersed fluorescence spectra. All indications are that SbH2 undergoes a dissociative process at low vibrational energies in the excited electronic state.

Guest Inclusion Modulates Concentration and Persistence of Photogenerated Radicals in Assembled Triphenylamine Macrocycles.

Substituted triphenylamine (TPA) radical cations show great potential as oxidants and as spin-containing units in polymer magnets. Their properties can be further tuned by supramolecular assembly. Here, we examine how the properties of photogenerated radical cations, intrinsic to TPA macrocycles, are altered upon their self-assembly into one-dimensional columns. These macrocycles consist of two TPAs and two methylene ureas, which drive the assembly into porous organic materials. Advantageously, upon activation the crystals can undergo guest exchange in a single-crystal-to-single-crystal transformation generating a series of isoskeletal host-guest complexes whose properties can be directly compared. Photoinduced electron transfer, initiated using 365 nm light-emitting diodes, affords radicals at room temperature as observed by electron paramagnetic resonance (EPR) spectroscopy. The line shape of the EPR spectra and the quantity of radicals can be modulated by both polarity and heavy atom inclusion of the encapsulated guest. These photogenerated radicals are persistent, with half-lives between 1 and 7 d and display no degradation upon radical decay. Re-irradiation of the samples can restore the radical concentration back to a similar maximum concentration, a feature that is reproducible over several cycles. EPR simulations of a representative spectrum indicate two species, one containing two N hyperfine interactions and an additional broad signal with no resolvable hyperfine interaction. Intriguingly, TPA analogues without bromine substitution also exhibit similar quantities of photogenerated radicals, suggesting that supramolecular strategies can enable more flexibility in stable TPA radical structures. These studies will help guide the development of new photoactive materials.

Electronic structure of non-KramersTb3+centers in garnet crystals and evidence of their energy and spin transfer toCe3+emitters

The electronic structure of non-Kramers ${\mathrm{Tb}}^{3+}$ centers in single crystals of yttrium aluminum garnet (YAG) was studied using a new-generation high-frequency magnetic resonance spectrometer that allows measurements of electron paramagnetic resonance (EPR), electron spin echo (ESE), the photon echo on hyperfine components of Stark levels in zero magnetic field, and optically detected magnetic resonance (ODMR). It was created on the basis of a highly stable microwave bridge operating in the near-terahertz region (0.094 or 0.130 THz), both in continuous-wave (cw) and pulse modes, a nonresonant system for supplying microwave power to a sample, and a cryogen-free magneto-optical cryostat. EPR, ESE, and cw measurements at two frequencies allowed us to reliably and with high accuracy determine the parameters of ${\mathrm{Tb}}^{3+}$ centers that occupy yttrium dodecahedral positions in YAG: ${g}_{||}=15.8\ifmmode\pm\else\textpm\fi{}0.2$, ${g}_{\ensuremath{\perp}}\ensuremath{\approx}0$ (|| corresponds to one of the $\ensuremath{\langle}100\ensuremath{\rangle}$ crystal axes), the zero-field splitting $\mathrm{\ensuremath{\Delta}}=2.705\ifmmode\pm\else\textpm\fi{}0.005\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$, and the hyperfine interaction constant $A=0.197\ifmmode\pm\else\textpm\fi{}0.005\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$. In addition to the ${\mathrm{Tb}}^{3+}$ centers in a regular environment, EPR spectra with lower intensity and a resolved hyperfine structure were found for at least three types of additional ${\mathrm{Tb}}^{3+}$ centers. They have symmetry, $g$ factors, and hyperfine interaction constants which are close to those of the main ${\mathrm{Tb}}^{3+}$ centers but differ in the zero-field splitting parameters \ensuremath{\Delta} that strongly depend on the crystal field. They were ascribed to ${\mathrm{Tb}}^{3+}$ centers with nearby antisite ${\mathrm{Y}}_{\mathrm{Al}}$ defects. Similarity with several types of ${\mathrm{Ce}}^{3+}$ centers in YAG crystals, the types, and relative concentrations of antisite defects are discussed. For one of the additional ${\mathrm{Tb}}^{3+}$ centers, splitting of the energy levels in the zero field turned out to be close to an energy of 94 GHz microwave quanta, and intense echo signals were observed in weak magnetic fields and in the zero field corresponding to the EPR transitions between the hyperfine components of the ${\mathrm{Tb}}^{3+}$ spin levels. ODMR spectra of ${\mathrm{Tb}}^{3+}$ centers in YAG crystals, containing Ce and Tb, were obtained by monitoring the intensity of the ${\mathrm{Ce}}^{3+}$ luminescence, which implies the transfer of energy from ${\mathrm{Tb}}^{3+}$ ions to ${\mathrm{Ce}}^{3+}$ ions with conservation of spin. This result seems to be important, since these systems are of interest for quantum communication and computations. Taking into account that cerium does not have isotopes with a nuclear spin and that terbium has 100% $^{159}\mathrm{Tb}$ having nuclear spin $I=3/2$ and a sufficiently large nuclear magnetic moment, the ${\mathrm{Tb}}^{3+}\ensuremath{-}{\mathrm{Ce}}^{3+}$ system in garnet crystals can be promising for coherent information processing. ${\mathrm{Tb}}^{3+}$ ions can play a role of qubits and ${\mathrm{Ce}}^{3+}$ ion with a lifetime of about 50 ns, and almost unity quantum efficiency of optical transitions can be used as a single-ion readout arrangement. The prospects for using this system as hardware for quantum communication and computations are discussed.

Structural properties of alumina-doped lithium borovanadate glasses and glass-ceramics

This study elucidates the role of Al2O3 in the lithium borovanadate (LBV) system, Li2O-B2O3-V2O5, in improving the glass-forming region of LBV glass. This increased glass-forming tendency is likely due to formation of [AlO4]− units. 11B, 27Al, and 51V nuclear magnetic resonance measurements suggest an importance of V-O-Al linkages and distribution of Li for charge compensation of [AlO4]− and [BO4]− units. Intense 51V NMR signals and resolved hyperfine coupling patterns in the electron paramagnetic resonance (EPR) spectra indicate that the majority of vanadium is pentavalent (V5+) and minor amounts of paramagnetic vanadium (V4+) are present. The EPR interaction parameters suggest that the vanadyl-like environments can be described as tetragonally compressed distorted octahedra. Based on V-2p3/2 X-ray photoelectron spectroscopy, the V4+ concentration is estimated at <3%. These vanadate glasses are attractive for energy storage applications, as they have higher specific capacities than commercial lithium-ion battery cathodes.

Optically pumped dynamic nuclear hyperpolarization in C13 -enriched diamond

We investigate nuclear spin hyperpolarization from nitrogen vacancy centers in isotopically enriched diamonds with $^{13}$C concentrations up to 100%. $^{13}$C enrichment leads to hyperfine structure of the nitrogen vacancy electron spin resonance spectrum and as a result the spectrum of dynamic nuclear polarization. We show that strongly-coupled $^{13}$C spins in the first shell surrounding a nitrogen vacancy center generate resolved hyperfine splittings, but do not act as an intermediary in the transfer of hyperpolarization of bulk nuclear spins. High levels of $^{13}$C enrichment are desirable to increase the efficiency of hyperpolarizaiton for magnetic resonance signal enhancement, imaging contrast agents, and as a platform for quantum sensing and many-body physics.