Nuclear Spin Flip Research Articles

A Paired-Ion Framework Composed of Vanadyl Porphyrin Molecular Qubits Extends Spin Coherence Times.

Molecular electron spin qubits arranged in precise arrays have great potential for use in quantum information science applications. Molecular qubits are synthetically versatile and can be placed in ordered arrangements upon incorporation into a new class of materials known as paired-ion frameworks (PIFs). A PIF composed of vanadyl porphyrin molecular qubits, VOTCPP-PIF-1, was synthesized as single crystals. Electron paramagnetic resonance spectroscopy was used to study their spin coherence at temperatures up to 293 K. A suspension of VOTCPP-PIF-1 at 5 K in dimethylformamide (DMF) had a spin-spin relaxation time (Tm) of 270 ns. In DMF-d7 and at 5 K, the coherence time of this material increased to 370 ns. This increase in Tm is attributed to the lower gyromagnetic ratio of 2H compared to 1H, which results in weaker electron-nuclear dipolar coupling that reduces the effect of nuclear spin flips on electron spin coherence. In toluene, crystals of VOTCPP-PIF-1 had a Tm of 31 ns at 293 K, demonstrating that PIFs are a promising platform for creating materials for quantum information science applications.

Rotational-Energy Transfer in H2 Ortho-Para Conversion on a Metal Surface: Interplay between Electron and Phonon Systems.

Clarifying energy transfer processes in molecular adsorption on solid surfaces is essential to understand the gas-surface interaction. Unlike the vibrational-energy transfer processes, which are thought to be well understood in detail, the rotational-energy transfer process still remains unclear. Considering the interconversion between ortho and para states of H2 is accompanied by the nuclear spin flip and the rotational-energy transfer, the surface-temperature dependence of the ortho-to-para conversion of molecularly chemisorbed H2 on Pd(210) is studied. The conversion rate is accelerated with an increase in surface temperature. Based on the conversion model proposed for metal surfaces, we analyze the temperature dependence of the conversion rate, taking into account both electron and phonon systems of the substrate. The rotational-energy transfer is most likely mediated by surface electrons with the assistance of the substrate phonons.

Using parity-nonconserving spin-spin coupling to measure the Tl nuclear anapole moment in a TlF molecular beam

An experiment utilizing a TlF molecular beam is being developed by the CeNTREX collaboration to search for hadronic interactions that violate both time-reversal ($\mathcal{T}$) and parity ($\mathcal{P}$) invariance. Here, we propose to use the same beam to look for a $\mathcal{T}$-invariance conserving but $\mathcal{P}$-nonconserving (PNC) effect induced by the anapole moment of the Tl nucleus, via a vector coupling of the two nuclear spins in TlF. To measure the nuclear anapole moment, the dc electric and magnetic fields in CeNTREX are replaced by rf fields resonant with a nuclear spin-flip transition. We adapt the relativistic coupled-cluster method in combination with relativistic density functional theory for the calculation of the molecular PNC spin-spin vector coupling constant that links the experimental signal with the anapole moment. The value of the $\mathcal{P}$-conserving spin-spin coupling constant calculated within the same approach is found to be in good agreement with available experimental data.

Rate constants for saturation-recovery EPR and ELDOR of 14N-Spin labels

Saturation-recovery (SR)-EPR can determine electron spin–lattice relaxation rates in liquids over a wide range of effective viscosity, making it especially useful for biophysical and biomedical applications. Here, I develop exact solutions for the SR-EPR and SR-ELDOR rate constants of 14N-nitroxyl spin labels as a function of rotational correlation time and spectrometer operating frequency. Explicit mechanisms for electron spin–lattice relaxation are: rotational modulation of the N-hyperfine and electron-Zeeman anisotropies (specifically including cross terms), spin-rotation interaction, and residual frequency-independent vibrational contributions from Raman processes and local modes. Cross relaxation from mutual electron and nuclear spin flips, and direct nitrogen nuclear spin–lattice relaxation, also must be included. Both the latter are further contributions from rotational modulation of the electron-nuclear dipolar interaction (END). All the conventional liquid-state mechanisms are defined fully by the spin-Hamiltonian parameters; only the vibrational contributions contain fitting parameters. This analysis gives a firm basis for interpreting SR (and inversion recovery) results in terms of additional, less standard mechanisms.

Shelving and latching spin readout in atom qubits in silicon

Singlet-triplet qubits typically require large magnetic field gradients on the order of militeslas to achieve high-fidelity electrically-controlled qubit operations. However, such large magnetic field gradients in quantum dot systems also increase charge noise and provide a relaxation pathway from the triplet to singlet qubit state, making high-fidelity readout challenging. Recently, shelving and latched readout have been employed in gate-defined quantum dots and donor-dot systems to achieve readout fidelities of 80% and 99.86%, respectively. In this paper, we theoretically examine shelving and latched singlet-triplet readout techniques for multidonor-based qubits in silicon where the large phosphorus hyperfine interaction of the order of 100 MHz gives rise to large effective magnetic field gradients (equivalent to tens of mT) but where it can change in time due to the presence of nuclear spin flips. Using numerical simulations, we show that shelving readout does not work giving a zero average visibility for mutidonor quantum dots, due to the time-varying nuclear spin polarization. To remedy this we propose adding a calibration step, in which we derive the nuclear spin polarization from a single shelving readout of a singlet state, before every qubit operation. The derived information can then be used via a feed-forward protocol to apply correct readout mapping, greatly improving the overall readout fidelity to $>99%$. We also simulate the latched readout mechanism, which is resistant to nuclear polarization changes and is thus promising for achieving high visibility readout. Here we observe a nonzero readout visibility irrespective of the nuclear spin flipping. Finally, we discuss how to optimize the readout visibility in the presence of strong hyperfine interactions and show that for both readout methods we can obtain readout fidelity $>99%$. These results demonstrate that singlet-triplet qubits based on multidonor quantum dots are a promising route for future electrically controlled qubits in silicon.

Kinetic approach to nuclear-spin polaron formation

Under optical cooling of nuclei, a strongly correlated nuclear-spin polaron state can form in semiconductor nanostructures with localized charge carriers due to the strong hyperfine interaction of the localized electron spin with the surrounding nuclear spins. Here we develop a kinetic-equation formalism describing the nuclear-spin polaron formation. We present a derivation of the kinetic equations for an electron-nuclear spin system coupled to reservoirs of different electron and nuclear spin temperatures which generate the exact thermodynamic steady state for equal temperatures independent of the system size. We illustrate our approach using the analytical solution of the central spin model in the limit of an Ising form of the hyperfine coupling. For homogeneous hyperfine coupling constants, i.e., the box model, the model is reduced to an analytically solvable form. Based on the analysis of the nuclear-spin distribution function and the electron-nuclear spin correlators, we derive a relation between the electron and nuclear spin temperatures, where the correlated nuclear-spin polaron state is formed. In the limit of large nuclear baths, this temperature line coincides with the critical temperature of the mean-field theory for polaron formation. The criteria of the polaron formation in a finite-size system are discussed. We demonstrate that the system's behavior at the transition temperature does not depend on details of the hyperfine-coupling distribution function but only on the effective number of coupled bath spins. In addition, the kinetic equations enable the analysis of the temporal formation of the nuclear-polaron state, where we find the build-up process predominated by the nuclear spin-flip dynamics.

Positive electronic exchange interaction and predominance of minor triplet channel in CIDNP formation in short lived charge separated states of D-X-A dyads.

Previous transient absorption measurements using the magnetically affected reaction yield (MARY) technique for a series of rigidly linked electron donor/electron acceptor dyads (D-X-A) consisting of a triarylamine donor, a naphthalene diimide acceptor, and a meta-conjugated diethynylbenzene unit as a bridge had revealed the presence of electronic exchange interaction, J, in the photoexcited charge separated (CS) state. Here, we present results obtained by photochemically induced dynamic nuclear polarization (photo-CIDNP) that allows for determining the sign of J. By variation of the magnetic field from 1 mT to 9.4 T, pronounced absorptive maxima of CIDNP were detected for more than 20 1H nuclei disregarding the sign of their hyperfine coupling constants in the transient charge separated state, with positions of maxima close to those found by the MARY technique. Quantitative comparison of the observed CIDNP signals for various D-X-A dyads reveals an increase in the CIDNP enhancement factor with increasing population of the triplet state determined by MARY spectroscopy at zero magnetic field. For CIDNP of the methyl groups of the TAA donor dyads, we found in all studies a good linear dependence between the CIDNP signal amplitude and the initial population of the CS triplet state. The linear relationship together with the absorptive CIDNP allows us to conclude that (i) the sign of the electronic exchange interaction Jex is positive, (ii) CIDNP is formed predominantly in the vicinity of level anticrossing between the T+ and S electronic levels, and (iii) coherent triplet-singlet transitions are induced by hyperfine interaction and accompanied by simultaneous electron and nuclear spin flip, T+β→Sα.

Single spin resonance driven by electric modulation of the g -factor anisotropy

We address the problem of electronic and nuclear spin resonance of an individual atom on a surface driven by a scanning tunnelling microscope. Several mechanisms have been proposed so far, some of them based on the modulation of exchange and crystal field associated to a piezoelectric displacement of the adatom driven by the RF tip electric field. Here we consider a new mechanism, where the piezoelectric displacement modulates the g factor anisotropy, leading both to electronic and nuclear spin flip transitions. We discuss thoroughly the cases of Ti-H (S = 1/2) and Fe (S = 2) on MgO, relevant for recent experiments. We model the system using two approaches. First, an analytical model that includes crystal field, spin orbit coupling and hyperfine interactions. Second, we carry out density functional based calculations. We find that the modulation of the anisotropy of the g tensor due to the piezoelectric displacement of the atom is an additional mechanism for STM based single spin resonance, that would be effective in S = 1/2 adatoms with large spin orbit coupling. In the case of Ti-H on MgO, we predict a modulation spin resonance frequency driven by the DC electric field of the tip.

Nuclear spin blockade of laser ignition of intramolecular rotation in the model boron rotor .

The boron rotor consists of a tri-atomic inner "wheel" that may rotate in its pseudo-rotating ten-atomic outer "bearing"-this concerted motion is called "contorsion." in its ground state has zero contorsional angular momentum. Starting from this initial state, it is a challenge to ignite contorsion by a laser pulse. We discover, however, that this is impossible, i.e., one cannot design any laser pulse that induces a transition from the ground to excited states with non-zero contorsional angular momentum. The reason is that the ground state is characterized by a specific combination of irreducible representations (IRREPs) of its contorsional and nuclear spin wavefunctions. Laser pulses conserve these IRREPs because hypothetical changes of the IRREPs would require nuclear spin flips that cannot be realized during the interaction with the laser pulse. We show that all excited target states of with non-zero contorsional angular momentum have different IRREPs that are inaccessible by laser pulses. Conservation of nuclear spins thus prohibits laser-induced transitions from the non-rotating ground to rotating target states. We discover various additional constraints imposed by conservation of nuclear spins, e.g., laser pulses can change clockwise to counter-clockwise contorsions or vice versa, but they cannot stop them. The results are derived in the frame of a simple model.

Efficient optical pumping using hyperfine levels in 145Nd3+:Y2SiO5 and its application to optical storage

Efficient optical pumping is an important tool for state initialization in quantum technologies, such as optical quantum memories. In crystals doped with Kramers rare-earth ions, such as erbium and neodymium, efficient optical pumping is challenging due to the relatively short population lifetimes of the electronic Zeeman levels, of the order of 100 ms at around 4 K. In this article we show that optical pumping of the hyperfine levels in isotopically enriched 145Nd :Y2SiO5 crystals is more efficient, owing to the longer population relaxation times of hyperfine levels. By optically cycling the population many times through the excited state a nuclear spin flip can be forced in the ground state hyperfine manifold, in which case the population is trapped for several seconds before relaxing back to the pumped hyperfine level. To demonstrate the effectiveness of this approach in applications we perform an atomic frequency comb memory experiment with 33% storage efficiency in 145Nd :Y2SiO5, which is on a par with results obtained in non-Kramers ions, e.g. europium and praseodymium, where optical pumping is generally efficient due to the quenched electronic spin. Efficient optical pumping in neodymium-doped crystals is also of interest for spectral filtering in biomedical imaging, as neodymium has an absorption wavelength compatible with tissue imaging. In addition to these applications, our study is of interest for understanding spin dynamics in Kramers ions with nuclear spin.

Tutorial: Novel properties of defects in semiconductors revealed by their vibrational spectra

This is an introductory survey of the vibrational spectroscopy of defects in semiconductors that contain light-mass elements. The capabilities of vibrational spectroscopy for the identification of defects, the determination of their microscopic structures, and their dynamics are illustrated by a few examples. Several additional examples are discussed, with a focus on defects with properties not obviously accessible by vibrational spectroscopy, such as the diffusivity of an impurity, the negative U ordering of electronic levels, and the time constant for a nuclear-spin flip. These novel properties have, nonetheless, been revealed by vibrational spectra and their interpretation by theory.

Electromagnetic dipole and Gamow-Teller responses of even and odd 90-94 40Zr isotopes in QRPA calculations with the D1M Gogny force

In this paper we present theoretical results on the dipole response in the proton spin-saturated 90-94Zr isotopes. The electric and magnetic dipole excitations are obtained in Hartree-Fock-Bogolyubov plus Quasi-particle Random Phase Approximation (QRPA) calculations performed with the D1M Gogny force. A pnQRPA charge exchange code is used to study the Gamow-Teller response. The results on the pygmy, the giant dipole resonances as well as those on the magnetic nuclear spin-flip excitation and the Gamow-Teller transitions are compared with available experimental or theoretical information. In our approach, the proton pairing plays a role in the phonon excitations, in particular in the M1 nuclear spin-flip resonance.

Magnon-induced nuclear relaxation in the quantum critical region of a Heisenberg linear chain

The low-temperature properties of spin-1/2 one-dimensional (1D) Heisenberg antiferromagnetic (HAF) chains which have relatively small exchange couplings between the spins can be tuned using laboratory-scale magnetic fields. Magnetization measurements, made as a function of temperature, provide phase diagrams for these systems and establish the quantum critical point (QCP). The evolution of the spin dynamics behavior with temperature and applied field in the quantum critical (QC) region, near the QCP, is of particular interest and has been experimentally investigated in a number of 1D HAFs using neutron scattering and nuclear magnetic resonance as the preferred techniques. In the QC phase both quantum and thermal spin fluctuations are present. As a result of extended spin correlations in the chains, magnon excitations are important at finite temperatures. An expression for the NMR spin-lattice relaxation rate $1/{T}_{1}$ of probe nuclei in the QC phase of 1D HAFs is obtained by considering Raman scattering processes which induce nuclear spin flips. The relaxation rate expression, which involves the temperature and the chemical potential, predicts scaling behavior of $1/{T}_{1}$ consistent with recent experimental findings for quasi-1D HAF systems. A simple relationship between $1/{T}_{1}$ and the deviation of the magnetization from saturation (${M}_{S}\ensuremath{-}M$) is predicted for the QC region.

Phonon-mediated nuclear spin relaxation in H2O

A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5–15 K. Temperature dependence of the rate is discussed in terms of the devised model.

Development of a 3He nuclear spin flip system on an in-situ SEOP 3He spin filter and demonstration for a neutron reflectometer and magnetic imaging technique

We have been developing a 3He neutron spin filter (NSF) using the spin exchange optical pumping (SEOP) technique. The 3He NSF provides a high-energy polarized neutron beam with large beam size. Moreover the 3He NSF can work as a π-flipper for a polarized neutron beam by flipping the 3He nuclear spin using a nuclear magnetic resonance (NMR) technique. For NMR with the in-situ SEOP technique, the polarization of the laser must be reversed simultaneously because a non-reversed laser reduces the polarization of the spin-flipped 3He. To change the polarity of the laser, a half-wavelength plate was installed. The rotation angle of the half-wavelength plate was optimized, and a polarization of 97% was obtained for the circularly polarized laser. The 3He polarization reached 70% and was stable over one week. A demonstration of the 3He nuclear spin flip system was performed at the polarized neutron reflectometer SHARAKU (BL17) and NOBORU (BL10) at J-PARC. Off-specular measurement from a magnetic Fe/Cr thin film and magnetic imaging of a magnetic steel sheet were performed at BL17 and BL10, respectively.

Real-time monitoring of Lévy flights in a single quantum system

L\'evy flights are random walks where the dynamics is dominated by rare events. Even though they have been studied in vastly different physical systems, their observation in a single quantum system has remained elusive. Here we analyze a periodically driven open central spin system and demonstrate theoretically that the dynamics of the spin environment exhibits L\'evy flights. For the particular realization in a single-electron charged quantum dot driven by periodic resonant laser pulses, we use Monte Carlo simulations to confirm that the long waiting times between successive nuclear spin flip events are governed by a power-law distribution; the corresponding exponent $\eta =-3/2$ can be directly measured in real-time by observing the waiting time distribution of successive photon emission events. Remarkably, the dominant intrinsic limitation of the scheme arising from nuclear quadrupole coupling can be minimized by adjusting the magnetic field or by implementing spin echo.

Submillisecond hyperpolarization of nuclear spins in silicon.

In this Letter, we devise a fast and effective nuclear spin hyperpolarization scheme, which is, in principle, magnetic field independent. We use this scheme to experimentally demonstrate polarizations of up to 66% for phosphorus donor nuclear spins in bulk silicon, which are created within less than 100 μs in a magnetic field of 0.35T at a temperature of 5K. The polarization scheme is based on a spin-dependent recombination process via weakly coupled spin pairs, for which the recombination time constant strongly depends on the relative orientation of the two spins. We further use this scheme to measure the nuclear spin relaxation time and find a value of ∼100 ms under illumination, in good agreement with the value calculated for nuclear spin flips induced by repeated ionization and deionization processes.

Hyperfine interactions of narrow-line trityl radical with solvent molecules

The electron nuclear dipolar interactions responsible for some dynamic nuclear polarization (DNP) mechanisms also are responsible for the presence formally in CW EPR spectra of forbidden satellite lines in which both the electron spin and a nuclear spin flip. Such lines arising from 1H nuclei are easily resolved in CW EPR measurements of trityl radicals, a popular family of DNP reagents. The satellite lines overlap some of the hyperfine features from 13C in natural abundance in the trityl radical, but their intensity can be easily determined by simple simulations of the EPR spectra using the hyperfine parameters of the trityl radical. Isotopic substitution of 2H for 1H among the hydrogens of the trityl radical and/or the solvent allows the dipolar interactions from the 1H on the trityl radical and from the solvent to be determined. The intensity of the dipolar interactions, integrated over all the 1H in the system, is characterized by the traditional parameter called reff. For the so-called Finland trityl in methanol, the reff values indicate that collectively the 1H in the unlabeled solvent have a stronger integrated dipolar interaction with the unpaired electron spin of the Finland trityl than do the 1H in the radical and consequently will be a more important DNP route. Although reff has the dimensions of distance, it does not correspond to any simple physical dimension in the trityl radical because the details of the unpaired electron spin distribution and the hydrogen distribution are important in the case of trityls.

Hyperfine structure of EPR spectra of Gd3+ odd isotopes in PbMoO4, Pb5Ge3O11, YVO4, and quadrupole interaction (temperature dependence)

A hyperfine structure of EPR signals of odd isotopes Gd3+ in Pb5Ge3O11, PbMoO4, and YVO4 single crystals has been investigated at different temperatures. The observation of forbidden (with the nuclear spin flip) transitions has made it possible to determine quadrupole interaction P20 associated with the gradient of the electric field of ligands at the impurity. It has been shown for the first time that, under the condition |P20| ≥ |Ax, y| (Ai are the tensor components), not only the magnitudes of splitting but also the observed asymmetry in a hyperfine structure (in perpendicular orientations of the magnetic field) depends on mutual signs of parameters of initial splitting b20 and P20. Results of studying the spectra have demonstrated that |b20(T)|/|P20(T)| ∼ const for a concrete single crystal, which assumes the similarity of physical mechanisms determining these parameters.

Monitoring nuclear spin-flip processes and measuring spin-diffusion constants via hole burning into the magnetization

An NMR experiment is presented for measuring spin-diffusion coefficients and observing homonuclear spin-flip processes. The magnetization is erased or even inverted in a multitude of spatially confined regions containing only one or a few spins (‘hole burning’). During the following time evolution of these holes, the following three time regimes can be observed: (i) local spin dynamics, (ii) spin diffusion towards a uniform average magnetization, and (iii) longitudinal nuclear magnetic relaxation. The oscillating characteristic of magnetization exchange between neighboring protons is demonstrated on a liquid crystal.