Anisotropic Hyperfine Research Articles

Spin Dynamics of Radical Pairs Using the Stochastic Schrödinger Equation in MolSpin.

The chemical reactivity of radical pairs is strongly influenced by the interactions of electronic and nuclear spins. A detailed understanding of these effects requires a quantum description of the spin dynamics that considers spin-dependent reaction rates, interactions with external magnetic fields, spin-spin interactions, and the loss of spin coherence caused by coupling to a fluctuating environment. Modeling real chemical and biochemical systems, which frequently involve radicals with multinuclear spin systems, poses a severe computational challenge. Here, we implement a method based on the stochastic Schrödinger equation in the software package MolSpin. Large electron-nuclear spin systems can be simulated efficiently, with asymmetric spin-selective recombination reactions, anisotropic hyperfine interactions, and nonzero exchange and dipolar couplings. Spin-relaxation can be modeled using the stochastic time-dependence of spin interactions determined by molecular dynamics and quantum chemical calculations or by allowing rate coefficients to be explicitly time-dependent. The flexibility afforded by this approach opens new avenues for exploring the effects of complex molecular motions on the spin dynamics of chemical transformations.

Morphology, physical, and structural aspects of copper nanoparticles induced- metal phosphate nanocompounds for gamma ray shielding and magnetic sensing applications

The inorganic nanocompounds were synthesized by solid state reaction with the composition 10Li2O+(30-x)Sb2O3 + xZnO + 59.5P2O5 + 0.5Cu (in mol%). SEM morphographs of the samples confirmed the grain size ≈0.5–2.5 μm. The EDAX spectra of the samples confirmed presence of copper (Cu) nanoparticles (<2 wt%) in the composition. The EDAX studies showed energy dispersion of Kα- photons by reactivity of elements P, Cu, and Zn, while the element Sb has shown dispersion of Lα- photons up to 10 keV. Mass attenuation coefficient (MAC) has exhibited a few discontinuities (bumps) at low energies (<10 keV) due to K, L- absorption edges of various elements (such as P, Cu, Zn, and Sb) presented in the samples. The shrinking of Phosphorous-Phosphorous separation (dP-P) from 4.716 Ao to 3.990 Ao indicated the greater solidity (or density) of the prepared nanocompounds at higher content of ZnO. XRD spectra showed the presence of major crystallites such as LiPO3, Li3PO4, Li6P6018, SbPO4, Cu3PO4, Cu2P2O7, Cu3[PO4]2, Zn[PO3]2, Zn2P2O7, ZnP4O11, and LiZnPO4 in the prepared nanocompounds. The average crystallite size was determined in the range of 35–83 nm. FTIR spectra of these compounds displayed the [PO2]−, [PO3]−, [PO4]3−, and [ZnO4] units along with linkages P─O─P, O─P─O, Sb─O─Sb, Cu─O─Cu, etc. A band due to vibrations of Cu─O bond has been observed in the range of 466–478 cm−1, which endorses the contribution of copper nanoparticles in the solid state reaction of the metal phosphate nanocompounds. A partially resolved hyperfine structure of magnetic resonance signals corresponding to g|| ≈2.4 and g⊥ ≈2.05 were observed due to the presence of an anisotropic hyperfine interaction of the electron spin (S = 1/2) with the nuclear spin (I = 3/2) of copper isotopes (63Cu and 65Cu) in the samples.

Hyperfine and Zeeman interactions in ultracold collisions of molecular hydrogen with atomic lithium.

We present a rigorous quantum scattering study of the effects of hyperfine and Zeeman interactions on cold Li-H2 collisions in the presence of an external magnetic field using a recent abinitio potential energy surface. We find that the low-field-seeking states of H2 predominantly undergo elastic collisions: the ratio of elastic-to-inelastic cross sections exceeds 100 for collision energies below 100 mK. Furthermore, we demonstrate that most inelastic collisions conserve the space-fixed projection of the nuclear spin. We show that the anisotropic hyperfine interaction between the nuclear spin of H2 and the electron spin of Li can have a significant effect on inelastic scattering in the ultracold regime, as it mediates two processes: the electron spin relaxation in lithium and the nuclear spin-electron spin exchange. Given the predominance of elastic collisions and the propensity of inelastic collisions to retain H2 in its low-field-seeking states, our results open up the possibility of sympathetic cooling of molecular hydrogen by atomic lithium, paving the way for future exploration of ultracold collisions and high-precision spectroscopy of H2 molecules.

Local structure of an oxygen impurity and fluorine vacancy complex in LiYF4

Crystal-growth defects and impurities are among the key factors limiting the performance of fluorine-based optical materials. This study reports the local structure of an oxygen impurity centre in LiYF4 single-crystal. Experimental electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy investigations were combined with first principle theoretical modelling to elucidate the defect structure. It was determined that, after irradiation with X-rays, an electron spin S=1/2 paramagnetic centre is generated. It is stable at room temperature and anneals above 150°C. The alignment of the g-tensor and magnitudes of hyperfine interactions suggest that the centre is an oxygen impurity and fluorine vacancy complex. Highly anisotropic hyperfine interaction with three fluorine atoms within 3 Å of the oxygen defect is observed. The results provide novel insights into oxygen ion incorporation in LiYF4 and are crucial to understanding and minimising radiation-induced degradation of the material.

Hyperfine-Resolved Rotational Spectroscopy of Phenyl Radical.

We present an analysis of the hyperfine-resolved rotational spectrum of gas-phase phenyl radical, c-C6H5, between 9 and 35 GHz. The isotropic and anisotropic hyperfine parameters of all five protons and the electronic spin-rotation fine structure parameters are accurately determined from this study, which allow detailed insight into the distribution and interactions of the unpaired electron in this prototypical σ-radical. The implications for laboratory and astronomical investigations of phenyl that are reliant on a precise centimeter-wave catalog are discussed, as are the prospects for detecting and assigning the hyperfine-resolved rotational spectra of other large, weakly polar hydrocarbon chain and ring radicals.

Stabilization of a flavoprotein for solid-state photo-CIDNP MAS NMR at room temperature by embedding in a glassy sugar matrix

Hyperpolarization via the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect can be detected in frozen solutions of electron transfer proteins generating a radical-pair upon illumination. The effect has been observed in various natural photosynthetic reaction centers and in light-oxygen-voltage (LOV) sensing domains incorporating a flavin mononucleotide (FMN) as chromophore. In LOV domains, where a highly conserved cysteine is mutated to a flavin to interrupt its natural photochemistry, a radical-pair is generated by electron transfer from a nearby tryptophan to the photoexcited triplet state of FMN. During the photocycle, both the LOV domain and the chromophore are photochemically degraded, e.g., by the formation of singlet oxygen. This limits the time for collection of hyperpolarized nuclear magnetic resonance (NMR) data. We show that embedding of the protein into a trehalose sugar glass matrix stabilizes the protein for 13C solid-state photo-CIDNP NMR experiments which can be conducted at room temperature in a powder sample. Additionally, this preparation allows for incorporation of high amounts of protein further boosting the intensity of the detected signals from FMN and tryptophan at natural abundance. Signal assignment is aided by quantum chemical calculations of absolute shieldings. The underlying mechanism for the surprising absorption-only signal pattern is not yet understood. Comparison to calculated isotropic hyperfine couplings imply that the enhancement is not due to the classical radical-pair mechanism (RPM). Analysis of the anisotropic hyperfine couplings associated with solid-state photo-CIDNP mechanisms also show no simple correlation, suggesting a more complex underlying mechanism.

Hyperfine interactions and coherent spin dynamics of isotopically purified 167Er3+ in polycrystalline Y2O3

167Er3+ doped solids are a promising platform for quantum technology due to erbium’s telecom C-band optical transition and its long hyperfine coherence times. We experimentally study the spin Hamiltonian and dynamics of 167Er3+ spins in Y2O3 using electron paramagnetic resonance (EPR) spectroscopy. The anisotropic electron Zeeman, hyperfine and nuclear quadrupole matrices are fitted using data obtained by X-band (9.5 GHz) EPR spectroscopy. We perform pulsed EPR spectroscopy to measure spin relaxation time T 1 and coherence time T 2 for the 3 principal axes of an anisotropic g tensor. Long electronic spin coherence time up to 24.4 μs is measured for lowest g transition at 4 K, exceeding previously reported values at much lower temperatures. Measurements of decoherence mechanism indicates T 2 limited by spectral diffusion and instantaneous diffusion. Long spin coherence times, along with a strong anisotropic hyperfine interaction makes 167Er3+:Y2O3 a rich system and an excellent candidate for spin-based quantum technologies.

Anisotropic Hyperfine Interaction of Surface-Adsorbed Single Atoms.

Hyperfine interactions have been widely used in material science, organic chemistry, and structural biology as a sensitive probe to local chemical environments. However, traditional ensemble measurements of hyperfine interactions average over a macroscopic number of spins with different geometrical locations and nuclear isotopes. Here, we use a scanning tunneling microscope (STM) combined with electron spin resonance (ESR) to measure hyperfine spectra of hydrogenated-Ti on MgO/Ag(100) at low-symmetry binding sites and thereby determine the isotropic and anisotropic hyperfine interactions at the single-atom level. Combining vector-field ESR spectroscopy with STM-based atom manipulation, we characterize the full hyperfine tensors of 47Ti and 49Ti and identify significant spatial anisotropy of the hyperfine interactions for both isotopes. Density functional theory calculations reveal that the large hyperfine anisotropy arises from highly anisotropic distributions of the ground-state electron spin density. Our work highlights the power of ESR-STM-enabled single-atom hyperfine spectroscopy in revealing electronic ground states and atomic-scale chemical environments.

Experimental Determination of a Single Atom Ground State Orbital through Hyperfine Anisotropy.

Historically, electron spin resonance (ESR) has provided excellent insight into the electronic, magnetic, and chemical structure of samples hosting spin centers. In particular, the hyperfine interaction between the electron and the nuclear spins yields valuable structural information about these centers. In recent years, the combination of ESR and scanning tunneling microscopy (ESR-STM) has allowed to acquire such information about individual spin centers of magnetic atoms bound atop a surface, while additionally providing spatial information about the binding site. Here, we conduct a full angle-dependent investigation of the hyperfine splitting for individual hydrogenated titanium atoms on MgO/Ag(001) by measurements in a vector magnetic field. We observe strong anisotropy in both the g factor and the hyperfine tensor. Combining the results of the hyperfine splitting with the symmetry properties of the binding site obtained from STM images and a basic point charge model allows us to predict the shape of the electronic ground state configuration of the titanium atom. Relying on experimental values only, this method paves the way for a new protocol for electronic structure analysis for spin centers on surfaces.

A comparative analysis of powder ENDOR spectra of aromatic and aliphatic radicals by exact and 1st order simulation

Exact and perturbation methods were employed in simulations of powder ENDOR spectra to obtain the anisotropic hyperfine ( hfc ) and nuclear quadrupole ( nqc ) coupling constants of certain organic radicals of interest in fundamental research and in applications in radiation research, surface chemistry and biophysics. The principal hfc values of the ring protons and methyl substituents for several aromatic cations trapped in disordered matrices might be more accurate than those previously reported using regular EPR. Only one of the earlier assignments of the naphthalene cation spectrum was in acceptable agreement with the simulations. The proton couplings at the β-position of alkyl radicals were deduced by simulations while the spectrum due to α-couplings with appreciable anisotropy was weak. Accurate simulation of the 14 N (I = 1) spectra in bio-radicals was obtained by adjustment of the relative orientation of the principal hfc and nuclear quadrupole coupling ( nqc ) tensors as well as the principal values. Adjustment of the excitation width parameter employed in the software was also required in a few cases to improve the agreement with the experimental spectra. The hfc patterns due to matrix nuclei ( 1 H and 7 Li) around the radicals of X-irradiated samples were simulated to elucidate the nature of the trapping sites in materials used for EPR dosimetry. ENDOR simulation programs known to us are presented in an Appendix. The performance of the ENDORF2 program used in previous works was examined by comparison with exact treatment. Input and output examples, source and executable codes used in this work can be downloaded at https://github.com/EndorF2/Simulation .

Nuclear-spin polaron formation: Anisotropy effects and quantum phase transition

We study theoretically the formation of the nuclear-spin polaron state in semiconductor nanosystems within the Lindblad equation approach. To this end, we derive a general Lindblad equation for the density operator that complies with the symmetry of the system Hamiltonian and address the nuclear-spin polaron formation for localized charge carriers subject to an arbitrarily anisotropic hyperfine interaction when optically cooling the nuclei. The steady-state solution of the density matrix for an anisotropic central spin model is presented as a function of the electron and nuclear spin bath temperature. Results for the electron-nuclear spin correlator as well as data for the nuclear spin distribution function serve as a measure of spin-entanglement. The features in both of them clearly indicate the formation of the nuclear polaron state at low temperatures where the crossover regime coincides with an enhancement of quantum fluctuations and agrees with the mean-field prediction of the critical temperature line. We can identify two distinct polaron states dependent upon the hyperfine anisotropy which are separated by a quantum phase transition at the isotropic point. These states are reflected in the temporal spin auto-correlation functions accessible in experiment via spin-noise measurements.

Site-Dependent Local Spin Susceptibility and Low-Energy Excitation in a Weyl Semimetal WTe2

Site-dependent local spin susceptibility is investigated with $^{125}$Te nuclear magnetic resonance in a Weyl semimetal WTe$_2$. The nuclear spin-lattice relaxation rate $1/T_1T$ shows a dependence of the square of temperature $T$ at high temperatures, followed by a constant behavior below 50 K. The temperature dependence features Weyl fermions appearing around the linearly crossing bands. The Knight shift $K$ scales to the square root of $1/T_1T$, corroborating a predominant spin contribution in low-lying excitation. The observed dependence of $K$ and $1/T_1T$ on the four Te sites shows the site-dependent electron correlation and density of states. The angular profile of the NMR spectrum gives the anisotropic hyperfine coupling tensor, consistent with $5p$ hole occupations on Te sites.

Stimuli-sensitivity and dynamics in the self-assembly structure of TEMPO-containing nonamphiphilic nanoparticles and their triggering hydrophobic drug release

Understanding the dynamics of stimuli-sensitive self-assembled nanomaterials is crucial for their potential applications, however, it is relatively difficult to quantitatively probe the dynamics using conventional analytical techniques because of the low sensitivity and selectivity of these techniques. In this research, TEMPO-containing nonamphiphilic copolymers are synthesized and highly sensitive, selective and non-destructive electron spin resonance (ESR) spectroscopy is applied to study their dynamics in stimuli-sensitive self-assembled nanostructures in different microenvironments. ESR spectroscopy reveals the structural changes of the smart supramolecular nanoparticles (SNPs) in their controlled assemblies by observing the molecular-level interactions. In order to obtain the dynamical evidence, several spectroscopic parameters such as rotational correlation time, hyperfine splitting constant, intensity increase/decrease and anisotropy parameters are determined from the ESR spectra. The stimuli-sensitivity and dynamics strongly depend on the SNPs’ microenvironment correlated to several chemical and physiological parameters such as radical concentration, pH, redox agent, temperature, polarity and viscosity. The results provide quantitative insights into the interface of the supramolecular assemblies. The nanoparticles showed good biocompatibility confirmed by the hemolysis test and the MTT assay. Furthermore, proof-of-concept experiments were carried out to demonstrate the SNPs’ stimuli-sensitive performance as a hydrophobic anticancer drug nanocarrier. This effort can be used to design other colloidal nano-platforms for the potential application in cancer treatment.

Mapping 13C hyperfine couplings and exchange interactions in short-lived charge separated states of rigid donor-bridge-acceptor dyads.

A detailed experimental study on reversible photo-induced intramolecular charge separation is presented based on nuclear magnetic resonance detection of chemically induced dynamic nuclear polarization. From variation of such polarization with the external magnetic field, the coupling constants of isotropic and anisotropic hyperfine interactions at individual 13C sites are measured in the short-lived charge separated state of dyad molecules composed of donor-bridge-acceptor parts. The objects of study were rigid donor-bridge-acceptor dyads, consisting of triarylamine as a donor, naphthalene diimide as an acceptor, and a meta-conjugated diethynylbenzene fragment as a bridge. By systematic variation of side groups in the bridging moiety, their influence on the electron withdrawing strength is traced. In combination with similar data for the 1H positions obtained previously for the same compounds [I. Zhukov et al., J. Chem. Phys. 152, 014203 (2020)], our results provide a reliable basis for the determination of the spin density distribution in the charge separated state of such dyads.

Spinning Molecules, Spinning Spins: Modulation of an Electron Spin Exchange Interaction in a Highly Anisotropic Hyperfine Field.

An investigation of spin and conformational dynamics in a series of symmetric Cu–Cu porphyrin dimer solutions is presented using electron paramagnetic resonance (EPR) spectroscopy. Previous spectral simulations focused on the isotropic exchange interaction (Javg) between the Cu centers. In this work, an additional line broadening parameter (Jmod) is explored in detail via variable temperature X-band EPR in liquid solution for several different structures. The Jmod phenomenon is due to fluctuations in the spin exchange interaction caused by conformational motion of the porphyrin planes. The Jmod parameter scales with the inverse of the rotational barriers that determine the Boltzmann-weighted torsional angle distribution between neighboring porphyrin planes. Arrhenius plots allow for extraction of the activation energies for rotation, which are 5.77, 2.84, and 5.31 kJ/mol for ethyne-bridged (porphinato)copper(II)-(porphinato)copper(II), butadiyne-bridged (porphinato)copper(II)-(porphinato)copper(II), and ethyne-bridged (porphinato)copper(II)-(porphinato)zinc(II)-(porphinato)copper(II) complexes, respectively. DFT calculations of these torsional barriers match well with the experimental results. This is the first report of a Jmod analysis within a highly anisotropic hyperfine field and demonstrates the utility of the theory for extraction of dynamic information.

Aminoxyl (nitroxyl or nitroxide) radical formation by the action of ozone on squalene containing secondary aromatic amine antioxidants

AbstractSqualene, a model compound of polyisoprene or natural rubber, was employed as solvent to study the reaction between ozone and a series of N,N′‐substituted‐p‐phenylenediamines (PPDs) and other secondary aromatic amines. In all cases, it was found that nitroxyl radicals were formed nearly quantitatively by the action of ozone on the squalene solutions containing dissolved the selected additives. The resulting nitroxyl radicals from PPDs or from other secondary aromatic amines were easily detected by electron spin resonance spectroscopy at room temperature and the isotropic and anisotropic hyperfine interaction constants of the said nitroxides were determined. The FT‐IR spectroscopy was employed to show the easy oxidation of unprotected squalene when exposed to an ozone stream, while in presence of PPDs, ozone is quantitatively scavenged by the PPDs forming the resulting nitroxides and protecting completely squalene from ozonolysis reactions. The nitroxyl radicals formed by PPDs or secondary aromatic amine ozonation exert a permanent antioxidant activity entering in a redox cycle already known to ensure a long flex fatigue life or the given rubber compound.

Impact of Chlorine Substitution on Electron Spin Relaxation of a Trityl Radical.

A perchlorotriarylmethyl tricarboxylic acid radical 99% enriched in 13C at the central carbon (13C1-PTMTC) was characterized in phosphate buffered saline solution (pH = 7.2) (PBS) at ambient temperature. Samples immobilized in 1:1 PBS:glycerol or in 9:1 trehalose:sucrose were studied as a function of temperature. Isotope enrichment at C1 creates a trityl that can be used to accurately measure microscopic viscosity. Understanding of the impact of the 13C hyperfine interaction on electron spin relaxation is important for application of this trityl in oximetry and distance measurements. The anisotropic 13C1 hyperfine couplings (Ax = Ay = 24 ± 2 MHz, Az = 200 ± 1 MHz) are larger than for the related 13C1-perdeuterated Finland trityl (13C1-dFT) and the g anisotropy (gx = 2.0013, gy = 2.0016, gz = 2.0042) is slightly larger than for 13C1-dFT. The tumbling correlation times (τR) for 13C1-PTMTC are 0.20 ± 0.02 ns in PBS and 0.40 ± 0.05 ns in 3:1 PBS:glycerol, which are shorter than for 13C1-dFT in the same solutions. T1 for 13C1-PTMTC is 3.5 ± 0.5 μs in PBS and 5.3 ± 0.4 μs in 3:1 PBS:glycerol, which are shorter than for 13C1-dFT due to faster tumbling, larger anisotropy of the 13C1 hyperfine, and about 30% larger contribution from the local mode. In immobilized samples T1 for 13C1-PTMTC is similar to that for 13C1-dFT and other trityls without chlorine or 13C1 substituents, indicating that the 13C1 and Cl substituents on the phenyl rings have little impact on T1. The temperature dependence of T1 was modeled with contributions from the direct, Raman, and local mode processes. Broadening of CW linewidths of about 0.6 G in fluid solution and about 2 G in rigid lattice is attributed to unresolved 35,37Cl hyperfine couplings.

Exploring the Role of the Central Carbide of the Nitrogenase Active-Site FeMo-cofactor through Targeted 13C Labeling and ENDOR Spectroscopy.

Mo-dependent nitrogenase is a major contributor to global biological N2 reduction, which sustains life on Earth. Its multi-metallic active-site FeMo-cofactor (Fe7MoS9C-homocitrate) contains a carbide (C4-) centered within a trigonal prismatic CFe6 core resembling the structural motif of the iron carbide, cementite. The role of the carbide in FeMo-cofactor binding and activation of substrates and inhibitors is unknown. To explore this role, the carbide has been in effect selectively enriched with 13C, which enables its detailed examination by ENDOR/ESEEM spectroscopies. 13C-carbide ENDOR of the S = 3/2 resting state (E0) is remarkable, with an extremely small isotropic hyperfine coupling constant, Ca = +0.86 MHz. Turnover under high CO partial pressure generates the S = 1/2 hi-CO state, with two CO molecules bound to FeMo-cofactor. This conversion surprisingly leaves the small magnitude of the 13C carbide isotropic hyperfine-coupling constant essentially unchanged, Ca = -1.30 MHz. This indicates that both the E0 and hi-CO states exhibit an exchange-coupling scheme with nearly cancelling contributions to Ca from three spin-up and three spin-down carbide-bound Fe ions. In contrast, the anisotropic hyperfine coupling constant undergoes a symmetry change upon conversion of E0 to hi-CO that may be associated with bonding and coordination changes at Fe ions. In combination with the negligible difference between CFe6 core structures of E0 and hi-CO, these results suggest that in CO-inhibited hi-CO the dominant role of the FeMo-cofactor carbide is to maintain the core structure, rather than to facilitate inhibitor binding through changes in Fe-carbide covalency or stretching/breaking of carbide-Fe bonds.

Performance of the DLPNO-CCSD and recent DFT methods in the calculation of isotropic and dipolar contributions to 14N hyperfine coupling constants of nitroxide radicals.

In the present study, the performance of a set of density functionals: BP86, PBE, OLYP, BEEF, PBEpow, TPSS, SCAN, PBEGXPBE, M06L, MN15L, B3LYP, PBE0, mPW1PW, B97, BHandHLYP, mPW1PW, B98, TPSS0, PBE1KCIS, SCAN0, M06, M06-2X, MN15, CAM-B3LYP, ωB97x, B2PLYP, and the B3LYP/N07D and PBE/N07D schemes in the calculation of the 14N anisotropic hyperfine coupling (HFC) constants of a set of 23 nitroxide radicals is evaluated. The results are compared with those obtained with the DLPNO-CCSD method and experimental HFC values. Harmonic contribution to the 14N HFC vibrational correction was calculated at the revPBE0/def2-TZVPP level and included in the evaluation. With the vibrational correction, the DLPNO-CCSD method yielded HFC values in good agreement with the experiment (mean absolute deviation (MAD) = 0.3G for the dipole-dipole contribution and MAD = 0.8G for the contact coupling contribution). The best DFT results are obtained using the M06 functional with MAD = 0.2G for the dipole-dipole contribution and MAD = 0.7G for the contact coupling contribution. In general, vibrational correction significantly improved most DFT functionals' performance but did not change its overall ranking.

The avian compass can be sensitive even without sustained electron spin coherence

Theoretical studies indicating the presence of long-lived coherence in the radical pair system have engendered questions about its utilitarian role in the avian compass. In this paper, we investigate the role of electron spin coherence in a multinuclear radical pair system including its impact on compass sensitivity. We find that sustenance of long-lived electron spin coherence is unlikely in a multinuclear hyperfine environment. After probing the role of the hyperfine interactions in the compass, we affirm the hyperfine anisotropy to be an essential parameter for the necessary sensitivity required for the compass action. Thereby, we identify a parameter regime where the compass would exhibit good sensitivity even without sustained electron spin coherence.