Electron Spin Pairing Research Articles

Mapping of valley splitting by conveyor-mode spin-coherent electron shuttling

In Si/SiGe heterostructures, the low-lying excited valley state seriously limits the operability and scalability of electron spin qubits. For characterizing and understanding the local variations in valley splitting, fast probing methods with high spatial and energy resolution are lacking. Leveraging the spatial control granted by conveyor-mode spin-coherent electron shuttling, we introduce a method for two-dimensional mapping of the local valley splitting by detecting magnetic field-dependent anticrossings of ground and excited valley states using entangled electron spin-pairs as a probe. The method has sub-μeV energy accuracy and a nanometer lateral resolution. The histogram of valley splittings spanning a large area of 210 nm by 18 nm matches well with statistics obtained by the established but time-consuming magnetospectroscopy method. For the specific heterostructure, we find a nearly Gaussian distribution of valley splittings and a correlation length similar to the quantum dot size. Our mapping method may become a valuable tool for engineering Si/SiGe heterostructures for scalable quantum computing.

Dynamic Nuclear Polarization Using Electron Spin Cluster.

Dynamic nuclear polarization (DNP) utilizing narrow-line electron spin clusters (ESCs) to achieve nuclear spin resonance matching (ESC-DNP) by microwave irradiation is a promising way to achieve NMR signal enhancements with a wide design scope requiring low microwave power at high magnetic field. Here we present the design for a trityl-based tetra-radical (TetraTrityl) to achieve DNP for 1H NMR at 7 T, supported by experimental data and quantum mechanical simulations. A slow-relaxing (T1e ≈ 1 ms) 4-ESC is found to require at least two electron spin pairs at <8 Å e-e spin distance to yield 1H ESC-DNP enhancement, while squeezing the rest of the e-e spin distances to <12 Å results in optimal 1H ESC-DNP enhancements. Fast-relaxing ESCs (T1e ≈ 10 μs) are found to require a weakly coupled narrow-line radical (sensitizer) to extract polarization from the ESC. These results provide design principles for achieving a power-efficient DNP at high field via ESC-DNP.

Theoretical examination of nuclear spin diffusion in light-induced spin coherences in photosystem I

Microsecond coherence times are predicted in spin dynamics calculations of a donor–acceptor electron spin pair P+A1A− created upon light excitation of photosystem I (PSI). The effects of nuclear spin diffusion (NSD) due to the anisotropic protein environment on the predicted coherence times TM are studied. Closely positioned pairs and triples of protons located 5–8 Å from the electron spin are shown to largely control TM. Knowledge of the crystal structure of PSI allows for spin dynamics calculations where specific cofactors and amino acid residues are removed or replaced and the identification of anisotropic environmental features controlling electronic decoherence. Finally, we show that NSD alone cannot explain the &amp;gt;3× shorter experimentally observed coherence times and suggest that methyl groups at key protein sites may explain this discrepancy.

Self-error-rejecting multipartite entanglement purification for electron systems assisted by quantum-dot spins in optical microcavities

We present a self-error-rejecting multipartite entanglement purification protocol (MEPP) for N-electron-spin entangled states, resorting to the single-side cavity-spin-coupling system. Our MEPP has a high efficiency containing two steps. One is to obtain high-fidelity N-electron-spin entangled systems with error-heralded parity-check devices (PCDs) in the same parity-mode outcome of three electron-spin pairs, as well as M-electron-spin entangled subsystems (2 ≤ M < N) in the different parity-mode outcomes of those. The other is to regain the N-electron-spin entangled systems from M-electron-spin entangled states utilizing entanglement link. Moreover, the quantum circuits of PCDs make our MEPP works faithfully, due to the practical photon-scattering deviations from the finite side leakage of the microcavity, and the limited coupling between a quantum dot and a cavity mode, converted into a failed detection in a heralded way.

Controlling the Dynamics of Three Electron Spin Qubits in a Donor-Acceptor-Radical Molecule Using Dielectric Environment Changes.

Photogenerated entangled electron spin pairs provide a versatile source of molecular qubits. Here, we examine the spin-dependent dynamics of a covalent donor-acceptor-radical molecule, D-A-R•, where the donor chromophore (D) is peri-xanthenoxanthene (PXX), the acceptor (A) is pyromellitimide (PI), and the radical (R•) is α,γ-bisdiphenylene-β-phenylallyl (BDPA). Selective photoexcitation of D within D-A-R• in butyronitrile/propionitrile at 140 K and butyronitrile at 105 K results in the spin-selective reactions D-A-R• → D•+-1(A•--R•) and D•+-3(A•--R•). Subsequently, at 140 K, D•+-1(A•--R•) → D•+-A-R-, whereas D•+-3(A•--R•) → D-A-R•. In contrast, at 105 K, D•+-3(A•--R•) → 3*D-A-R• and D-A-R•. Time-resolved EPR spectroscopy shows that 3*D-A-R• is highly spin-polarized, where the ms = ±1/2 spin sublevels of the doublet-quartet manifolds are selectively populated. These results demonstrate dielectric environment control over different spin states in the same molecule.

Magnetic Control of the Earthquakes

Many observations reliably exhibit correlations between the magnetic perturbations and seismic responses, convincing that the magneto-seismicity is not a myth. Magnetic control of the earthquakes is based on physics of magneto-plasticity, the remarkable phenomenon, which implies generation of the electron spin pairs on the trapped dislocations, in which Coulomb interaction is switched off. Microwave irradiation at Zeeman frequencies in these pairs stimulates the motion of dislocations, inducing release of elastic energy into the safe plastic deformation. Magneto-seismic correlations unambiguously demonstrate that the earthquakes are indeed suppressed by low-frequency (wide and continuous spectrum from Hz to MHz) microwaves The detailed mechanism of this phenomenon is discussed and experimental proofs are given in terms of magneto-plasticity as a feasible means to control earthquakes.

The GHSZ Argument: A Gedankenexperiment Requiring More Denken.

I reassess the gedankenexperiment of Greenberger, Horne, Shimony, and Zeilinger after twenty-five years, finding their influential claim to the discovery of an inconsistency inherent in high dimensional formulations of local realism to arise from a fundamental error of logic. They manage this by presuming contradictory premises: that a specific linear combination of four angles involved in their proposed parallel experiments on two pairs of electrons equals both and 0 at the same time. Ignoring this while presuming the contradictory implications of these two conditions, they introduce the contradiction themselves. The notation they use in their “derivation” is not sufficiently ornate to represent the entanglement in the double electron spin pair problem they design, confounding their error. The situation they propose actually motivates only an understanding of the full array of symmetries involved in their problem. In tandem with the error now recognised in the supposed defiance of Bell’s inequality by quantum probabilities, my reassessment of their work should motivate a reevaluation of the current consensus outlook regarding the principle of local realism and the proposition of hidden variables.

Molecule-made electron spin pair executes quantum gate

Donor-chromophore-acceptor molecule generates an electron spin pair that can run a controlled-NOT gate, a critical step on the path to realizing quantum computing.

Photodriven quantum teleportation of an electron spin state in a covalent donor-acceptor-radical system.

Quantum teleportation transfers the quantum state of a system over an arbitrary distance from one location to another through the agency of quantum entanglement. Because quantum teleportation is essential to many aspects of quantum information science, it is important to establish this phenomenon in molecular systems whose structures and properties can be tailored by synthesis. Here, we demonstrate electron spin state teleportation in an ensemble of covalent organic donor-acceptor-stable radical (D-A-R•) molecules. Following preparation of a specific electron spin state on R• in a magnetic field using a microwave pulse, photoexcitation of A results in the formation of an entangled electron spin pair D•+-A•-. The spontaneous ultrafast chemical reaction D•+-A•--R• → D•+-A-R- constitutes the Bell state measurement step necessary to carry out spin state teleportation. Quantum state tomography of the R• and D•+ spin states using pulse electron paramagnetic resonance spectroscopy shows that the spin state of R• is teleported to D•+ with high fidelity.

(Invited) On the Active Sites in the Graphene-Catalyzed Oxygen Reduction Reaction

A critical issue in the impressive worldwide fuel cell research efforts is the possibility of using graphene-based materials in the oxygen reduction reaction (ORR). In the overwhelming literature that has accumulated, much controversy (and even more confusion) exists regarding some of the essential aspects of the reaction mechanism. A consensus can emerge only if interpretations of the abundant experimental evidence are consistent with what is known about the behavior of graphene-based materials, both the novel and the traditional ones, as catalysts in the absence of an electric field, as well as with the well understood gas-phase behavior of sp2-hybridized carbon materials in the presence of dioxygen. From this standpoint, the key issue is whether a reasonable and instructive analogy exists between the mechanism of electron-transfer catalysis on the carbon surface, e- + C(O2) = C(O2 -) C(O2 -) + H2O(aq) = OH-(aq) + C(OOH) C(OOH) = C=O + OH, and the proposed mechanism of electrocatalysis: Ar-C: + O2 → Ar-C(O2) Ar-C(O2) + H+(aq) → Ar-C(OOH) Ar-C(OOH) → Ar-C + HO2 - A clarification can be sought by analyzing the results of the search for ever more effective (electro)catalysts. In this context, structural modifications of the graphene surface are particularly enlightening. Thus, for example, the superior electrocatalytic activity of nitrogen-doped graphene is attributed to the presence of either quaternary or pyridinic nitrogen. Boron is of interest as well, if for nothing else then for its contribution of one electron less than the carbon atoms to graphene’s pi-system. And the presence, or formation, of an embedded MN4 moiety – where M is most often a transition metal such as cobalt or iron – is also of great interest because of the obvious analogy with porphyrin or phthalocyanine structures. Using a heretofore unexplored approach to examine these widely varying graphene-based surfaces, and unifying the evidence based on density functional theory, a compelling case is presented here for the experimentally elusive identification of the active sites (AS) that are responsible for the technologically and economically crucial electron transfer at the fuel cell cathode: AS + O2 + 4e-(aq) + 4H+(aq) = AS + 2H2O. It is also argued, not unexpectedly, that these are essentially the same sites at which analogous oxygen transfer processes - carbon oxidation/combustion, graphene functionalization and oxygen spillover - also occur. Their thermodynamic driving force is shown to be crucially dependent on the details of the electron density distribution and spin pairing processes at the active sites and in their vicinity.

Biradical rotamer states tune electron J coupling and MAS dynamic nuclear polarization enhancement

Cross Effect (CE) Dynamic Nuclear Polarization (DNP) relies on the dipolar (D) and exchange (J) coupling interaction between two electron spins. Until recently only the electron spin D coupling was explicitly included in quantifying the DNP mechanism. Recent literature discusses the potential role of J coupling in DNP, but does not provide an account of the distribution and source of electron spin J coupling of commonly used biradicals in DNP. In this study, we quantified the distribution of electron spin J coupling in AMUPol and TOTAPol biradicals using a combination of continuous wave (CW) X-band electron paramagnetic resonance (EPR) lineshape analysis in a series of solvents and at variable temperatures in solution – a state to be vitrified for DNP. We found that both radicals show a temperature dependent distribution of J couplings, and the source of this distribution to be conformational dynamics. To qualify this conformational dependence of J coupling in both molecules we carry out Broken Symmetry DFT calculations which show that the biradical rotamer distribution can account for a large distribution of J couplings, with the magnitude of J coupling directly depending on the relative orientation of the electron spin pair. We demonstrate that the electron spin J couplings in both AMUPol and TOTAPol span a much wider distribution than suggested in the literature. We affirm the importance of electron spin J coupling for DNP with density matrix simulations of DNP in Liouville space and under magic angle spinning, showcasing that a rotamer with high J coupling and optimum relative g-tensor orientation can significantly boost the DNP performance compared to random orientations of the electron spin pair. We conclude that moderate electron spin J coupling above a threshold value can facilitate DNP enhancements.

Microwave stimulation of dislocations and the magnetic control of the earthquake core

Microwave irradiation transforms the elasticity of solids into plasticity by controlling the dislocation mobility via magnetic interactions within the electron spin pairs on the dislocations. In ionic crystals, microwaves cause dislocations to accelerate and increase their mean free path, thus leading to a release of elastic energy; in covalent crystals, microwaves keep dislocations in place, thereby accumulating elastic energy and increasing the crystal strength. Microwave pumping at resonant Zeeman frequencies (in the magnetic resonance regime) is firm evidence of the concepts of electron spin pairs and of the magnetoplasticity phenomenon itself. However, the dominant contribution to the macroscopic transformation of elastic energy into plastic flow comes from nonresonant microwaves. These can be used to control the mechanics of diamagnetic solids, including, importantly, the earthquake focus. The observed correlation between magnetic events (such as magnetic storms and hydrodynamically generated high-power magnetic pulses) and their seismic and tectonic consequences (earthquake frequency and magnitude and deformations) indicates unambiguously that magnetically controlling the earthquake focus provides a realistic means to prevent a catastrophe by transforming large-magnitude earthquakes into weak, low-magnitude events.

Signatures of long-range spin-spin interactions in an (In,Ga)As quantum dot ensemble

We present an investigation of the electron spin dynamics in an ensemble of singly-charged quantum dots subject to an external magnetic field and laser pumping with circularly polarized light. The spectral laser width is tailored such that different groups of quantum dots are coherently pumped. Surprisingly, the dephasing time $T^*$ of the electron spin polarization depends only weakly on the laser spectral width. These findings can be consistently explained by a cluster theory of coupled quantum dots with a long range electronic spin-spin interaction. We present a numerical simulation of the spin dynamics based on the central spin model that includes a quantum mechanical description of the laser pulses as well as a time-independent Heisenberg interaction between each pair of electron spins. We discuss the individual dephasing contributions stemming from the Overhauser field, the distribution of the electron $g$-factors and the electronic spin-spin interaction as well as the spectral width of the laser pulse. This analysis reveals the counterbalancing effect of the total dephasing time when increasing the spectral laser width. On one hand, the deviations of the electron $g$-factors increase. On the other hand, an increasing number of coherently pumped electron spins synchronize due to the spin-spin interaction. We find an excellent agreement between the experimental data and the dephasing time in the simulation using an exponential distribution of Heisenberg couplings with a mean value $\overline{J}\approx 0.26\,\mathrm{\mu eV}$.

Sensing Coherent Dynamics of Electronic Spin Clusters in Solids.

We observe coherent spin exchange between identical electronic spins in the solid state, a key step towards full quantum control of electronic spin registers in room temperature solids. In a diamond substrate, a single nitrogen vacancy (NV) center coherently couples to two adjacent S=1/2 dark electron spins via the magnetic dipolar interaction. We quantify NV-electron and electron-electron couplings via detailed spectroscopy, with good agreement to a model of strongly interacting spins. The electron-electron coupling enables an observation of coherent flip-flop dynamics between electronic spins in the solid state, which occur conditionally on the state of the NV. Finally, as a demonstration of coherent control, we selectively couple and transfer polarization between the NV and the pair of electron spins. Our observations enable the realization of fast quantum gate operations and quantum state transfer in a scalable, room temperature, quantum processor.

High-pressure spectroscopic study of siderite (FeCO3) with a focus on spin crossover

Fe-bearing carbonates have been proposed as possible candidate host minerals for carbon inside the Earth’s interior and hence their spectroscopic properties can provide constraints on the deep carbon cycle. Here we investigate high-pressure spin crossover in synthetic FeCO 3 (siderite) using a combination of Mossbauer, Raman, and X-ray absorption near edge structure spectroscopy in diamond-anvil cells. These techniques sensitive to the short-range atomic environment show that at room temperature and under quasi-hydrostatic conditions, spin crossover in siderite takes place over a broad pressure range, between 40 and 47 GPa, in contrast to previous X-ray diffraction data that described the transition as a sharp volume collapse at approximately 43 GPa. Based on these observations we consider electron spin pairing in siderite to be a dynamic process, where Fe atoms can be either high spin or low spin in the crossover region. Mode Gruneisen parameters extracted from Raman spectra collected at pressures below and above spin crossover show a drastic change in stiffness of the Fe-O octahedra after the transition, where they become more compact and hence less compressible. Mossbauer experiments performed on siderite single crystals as well as powder samples demonstrate the effect of differential stress on the local structure of siderite Fe atoms in a diamond-anvil cell. Differences in quadrupole splitting values between powder and single crystals show that local distortions of the Fe site in powder samples cause spin crossover to start at higher pressure and broaden the spin crossover pressure range.

Coherence Transfer by Passage Pulses in Electron Paramagnetic Resonance Spectroscopy.

Linear passage pulses provide a simple approach to ultra-wideband electron paramagnetic resonance (EPR) spectroscopy. We show by numerical simulations that the efficiency of inversion of polarization or coherence order on a single transition by idealized passage pulses is an exponential function of critical adiabaticity during passage, which allows for defining an effective flip angle for fast passage. This result is confirmed by experiments on E' centers in Herasil glass. Deviations from the exponential law arise due to relaxation and a distribution of the adiabaticity parameter that comes from inhomogeneity of the irradiation field. Such inhomogeneity effects as well as edge effects in finite sweep bands cause a distribution of dynamic phase shifts, which can be partially refocused in echo experiments. In multilevel systems, passage of several transitions leads to generation of coherence on formally forbidden transitions that can also be described by the concept of an effective flip angle. On the one hand, such transfer to coherence on forbidden transitions is a significant magnetization loss mechanism for dipole-dipole coupled electron spin pairs at distances below about 2 nm. On the other hand, it can potentially be harnessed for electron spin echo envelope modulation (ESEEM) experiments, where matching of the irradiation field strength to the nuclear Zeeman frequency leads to efficient generation of nuclear coherence and efficient back transfer to electron coherence on allowed transitions at high adiabaticity.

Electronegativity, Hardness and Atomic number: Mutual relationships explored via novel isoelectronic series methodology

The novel isoelectronic methodology proposed recently, reveals electronic configuration dependent relationship between the hardness and atomic number, and electronegativity and hardness. In eight out of the first ten isoelectronic series, the hardness measure (I-A)/2 is an excellent linear function of atomic number (Z), and the electronegativity measure, (I+A)/2 is a quadratic function of the hardness measure; Hence, it is inferred that hardness (η) is proportional to atomic number (η α Z) and electronegativity (χ) is proportional to square of hardness (χ α η2). In both the cases, the two inert gas series species are the exceptions where η α Z2 and χ α η, respectively. These relationships are slightly in discord with the previously reported mutual connections. Previous reports do not indicate electronic configuration dependency as well. The linear (I-A)/2 versus Z plots arises as a result of cancellation of Z2 terms, and the slopes of these plots are sensitive indicator of the electron spin pairing and orbital change. A potential use of (I-A)/2 versus Z, and (I+A)/2 versus (I-A)/2 plots in pointing the incorrect ionization potentials and their evaluation has been elaborated by the striking example of the sixth ionization potential of phosphorous. The (I-A)/2 versus Z relations also provides us a new way to obtain hardness values of cationic and anionic atomic species.

Probing long-range carrier-pair spin-spin interactions in a conjugated polymer by detuning of electrically detected spin beating.

Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm.

Investigation of the electronic ground states for a reduced pyridine(diimine) uranium series: evidence for a ligand tetraanion stabilized by a uranium dimer.

The electronic structures of a series of highly reduced uranium complexes bearing the redox-active pyridine(diimine) ligand, (Mes)PDI(Me) ((Mes)PDI(Me) = 2,6-(2,4,6-Me3-C6H2-N═CMe)2C5H3N) have been investigated. The complexes, ((Mes)PDI(Me))UI3(THF) (1), ((Mes)PDI(Me))UI2(THF)2 (2), [((Mes)PDI(Me))UI]2 (3), and [((Mes)PDI(Me))U(THF)]2 (4), were examined using electronic and X-ray absorption spectroscopies, magnetometry, and computational analyses. Taken together, these studies suggest that all members of the series contain uranium(IV) centers with 5f (2) configurations and reduced ligand frameworks, specifically [(Mes)PDI(Me)](•/-), [(Mes)PDI(Me)](2-), [(Mes)PDI(Me)](3-) and [(Mes)PDI(Me)](4-), respectively. In the cases of 2, 3, and 4 no unpaired spin density was found on the ligands, indicating a singlet diradical ligand in monomeric 2 and ligand electron spin-pairing through dimerization in 3 and 4. Interaction energies, representing enthalpies of dimerization, of -116.0 and -144.4 kcal mol(-1) were calculated using DFT for the monomers of 3 and 4, respectively, showing there is a large stabilization gained by dimerization through uranium-arene bonds. Highlighted in these studies is compound 4, bearing a previously unobserved pyridine(diimine) tetraanion, that was uniquely stabilized by backbonding between uranium cations and the η(5)-pyridyl ring.

Diamond-based single-molecule magnetic resonance spectroscopy

The detection of a nuclear spin in an individual molecule represents a key challenge in physics and biology whose solution has been pursued for many years. The small magnetic moment of a single nucleus and the unavoidable environmental noise present the key obstacles for its realization. In this paper, we demonstrate theoretically that a single nitrogen-vacancy center in diamond can be used to construct a nano-scale single-molecule spectrometer that is capable of detecting the position and spin state of a single nucleus and can determine the distance and alignment of a nuclear or electron spin pair. The proposed device would find applications in single-molecule spectroscopy in chemistry and biology, for example in determining the protein structure or in monitoring macromolecular motions, and can thus provide a tool to help unravel the microscopic mechanisms underlying bio-molecular function.