Electron-nuclear Interaction Research Articles

Nuclear spin-lattice relaxation in carbon nanostructures

Abstract Interpretation of nuclear spin-lattice relaxation data in the carbon nanostructures is usually based on the analysis of fluctuations of dipole–dipole interactions of nuclear spins and anisotropic electron–nuclear interactions responsible for chemical shielding, which are caused by molecular dynamics. However, many nanocarbon systems such as fullerene and nanotube derivatives, nanodiamonds and carbon onions reveal noticeable amount of paramagnetic defects with unpaired electrons originating from dangling bonds. The interaction between nuclear and electron spins strongly influences the nuclear spin-lattice relaxation, but usually is not taken into account, thus the relaxation data are not correctly interpreted. Here we report on the temperature dependent NMR spectra and spin-lattice relaxation measurements of intercalated fullerenes C 60 ( MF 6 ) 2 ( M =As and Sb), where nuclear relaxation is caused by both molecular rotation and interaction between nuclei and unpaired electron spins. We present a detailed theoretical analysis of the spin-lattice relaxation data taking into account both these contributions. Good agreement between the experimental data and calculations is obtained. The developed approach would be useful in interpreting the NMR relaxation data in different nanostructures and their intercalation compounds.

Structure and Function of Quinones in Biological Solar Energy Transduction: A Differential Pulse Voltammetry, EPR, and Hyperfine Sublevel Correlation (HYSCORE) Spectroscopy Study of Model Benzoquinones

Quinones are widely used electron transport cofactors in photosynthetic reaction centers. Previous studies have suggested that the structure of the quinone cofactors and the protein interactions or "smart" matrix effects from the surrounding environment govern the redox potential and hence the function of quinones in photosynthesis. In the present study, a series of 1,4-benzoquinone models are examined via differential pulse voltammetry to provide relative redox potentials. In parallel, CW and pulsed EPR methods are used to directly determine the electronic properties of each benzoquinone in aprotic and protic environments. The shifts in the redox potential of the quinones are found to be dependent on the nature of the substituent group and the number of substituent groups on the quinone molecule. Further, we establish a direct correlation between the nature of the substituent group and the change in electronic properties of the benzosemiquinone by analysis of the isotropic and anisotropic components of the electron-nuclear hyperfine interactions observed by CW and pulsed EPR studies, respectively. Examination of an extensive library of model quinones in both aprotic and protic solvents indicates that hydrogen-bonding interactions consistently accentuate the effects of the substituent groups of the benzoquinones. This study provides direct support for the tuning and control of quinone cofactors in biological solar energy transduction through interactions with the surrounding protein matrix.

Electron spin-lattice relaxation in solid ethanol: Effect of nitroxyl radical hydrogen bonding and matrix disorder

The electron spin-lattice relaxation of TEMPO and TEMPONE was measured at temperatures between 5 and 80 K in crystalline and glassy ethanol using X-band electron paramagnetic resonance spectroscopy. The experimental data at the lowest temperatures studied were explained in terms of electron-nuclear dipolar interaction between the paramagnetic center and the localized excitations, whereas at higher temperatures low-frequency vibrational modes from the host matrix and Raman processes should be considered. The strong impact of hydrogen bonding between the dopant molecule and ethanol host on the spin relaxation was observed in ethanol glass whereas in crystalline ethanol both paramagnetic guest molecules behaved similarly.

Electron-nuclear double resonance study of [formula omitted] ions in [formula omitted] crystals

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify and characterize V 4+ ions in a bulk single crystal of vanadium dioxide (V O 2). These S = 1 / 2 defects are observed in the as-grown crystal because an adjacent nonmagnetic M 4+ impurity, e.g., a Si 4+ ion, has destroyed the normal antiferromagnetic coupling associated with the close pairs of V 4+ ions that occur in the low-temperature monoclinic phase of V O 2. EPR spectra taken near 5 K with the magnetic field along the [110] and [001] axes show resolved hyperfine patterns due to one 51V nucleus. ENDOR spectra taken at 5 K with the magnetic field parallel to the [001] axis have large nuclear electric quadrupole splittings as a result of a significant electric field gradient at the 51V nucleus. Spin-Hamiltonian parameters describing the electron Zeeman, hyperfine, and nuclear electric quadrupole interactions are reported.

Two-center interference effects on the electron capture process by alpha particles from molecular hydrogens

The single-electron capture process in the collision of fast alpha particles with hydrogen molecules is treated using the first-order Born approximation with correct boundary conditions. The results are obtained by considering both the inter-nuclear and nuclear–electronic interactions and by employing a Hartree–Fock molecular wave function. Double differential cross sections are evaluated for the electron capture from a molecular target with a fixed orientation. In the fixed-nuclei approximation, the differential cross sections are calculated for an equally-weighted averaging over all molecular orientations. The interference patterns, due to the scattering from two atomic centers, are apparent in different forms both in the double differential cross sections and in the cross sections as a function of the angle between the molecular axis and the incident direction. Integrated cross sections are calculated and compared with other theoretical and experimental results.

Recent progress in approximate self-consistent-field theory

Progress in the development of self-consistent molecular-orbital methods for all valence electrons using zero differential overlap approximations is reviewed. Calculations of equilibrium bond lengths, bond angles, bending force constants, electric dipole moments and electron-nuclear hyperfine interactions are shown to be in moderately good agreement with experiment for a wide range of molecules and free radicals.

Hole–spin dephasing time associated with hyperfine interaction in quantum dots

The spin interaction of a hole confined in a quantum dot with the surrounding nuclei is described in terms of an effective magnetic field. We show that, in contrast to the Fermi contact hyperfine interaction for conduction electrons, the dipole-dipole hyperfine interaction is anisotropic for a hole, for both pure or mixed hole states. We evaluate the coupling constants of the hole-nuclear interaction and demonstrate that they are only 1 order of magnitude smaller than the coupling constants of the electron-nuclear interaction. We also study, theoretically, the hole--spin dephasing of an ensemble of quantum dots via the hyperfine interaction in the framework of frozen fluctuations of the nuclear field, in the absence or in the presence of an applied magnetic field. We also discuss experiments which could evidence the dipole-dipole hyperfine interaction and give information on hole mixing.

Electron–nuclear interaction in 13C nanotube double quantum dots

Hyperfine coupling to nuclei can be detrimental to the coherence of electron spins, but properly harnessed it can provide a mechanism for manipulation and storage of quantum information. Spin-blockade measurements in 13C carbon nanotubes now show surprisingly strong effects of electron–nuclear interaction, with a hyperfine coupling two orders of magnitude larger than previously anticipated. For coherent electron spins, hyperfine coupling to nuclei in the host material can either be a dominant source of unwanted spin decoherence1,2,3 or, if controlled effectively, a resource enabling storage and retrieval of quantum information4,5,6,7. To investigate the effect of a controllable nuclear environment on the evolution of confined electron spins, we have fabricated and measured gate-defined double quantum dots with integrated charge sensors made from single-walled carbon nanotubes with a variable concentration of 13C (nuclear spin I=1/2) among the majority zero-nuclear-spin 12C atoms. We observe strong isotope effects in spin-blockaded transport, and from the magnetic field dependence estimate the hyperfine coupling in 13C nanotubes to be of the order of 100 μeV, two orders of magnitude larger than anticipated8,9. 13C-enhanced nanotubes are an interesting system for spin-based quantum information processing and memory: the 13C nuclei differ from those in the substrate, are naturally confined to one dimension, lack quadrupolar coupling and have a readily controllable concentration from less than one to 105 per electron.

Polynomial-time quantum algorithm for the simulation of chemical dynamics

The computational cost of exact methods for quantum simulation using classical computers grows exponentially with system size. As a consequence, these techniques can be applied only to small systems. By contrast, we demonstrate that quantum computers could exactly simulate chemical reactions in polynomial time. Our algorithm uses the split-operator approach and explicitly simulates all electron-nuclear and interelectronic interactions in quadratic time. Surprisingly, this treatment is not only more accurate than the Born-Oppenheimer approximation but faster and more efficient as well, for all reactions with more than about four atoms. This is the case even though the entire electronic wave function is propagated on a grid with appropriately short time steps. Although the preparation and measurement of arbitrary states on a quantum computer is inefficient, here we demonstrate how to prepare states of chemical interest efficiently. We also show how to efficiently obtain chemically relevant observables, such as state-to-state transition probabilities and thermal reaction rates. Quantum computers using these techniques could outperform current classical computers with 100 qubits.

Nuclear Relaxometry Helps Designing Systems for Solution DNP on Proteins

The measurement of water proton longitudinal relaxation rates in aqueous solutions of paramagnetic compounds (radicals, paramagnetic metal ions) as a function of magnetic field (relaxometry) provides two important pieces of information for predicting the efficacy of dynamic nuclear polarization (DNP) to be ultimately achieved on protein nuclei: the correlation time for the electron–nuclear interaction and the actual water proton relaxation rate at any magnetic field of interest. Likewise, relaxometry measurements on protein protons themselves, which can be performed in D2O solutions, provide information on the polarization loss occurring on protein protons in DNP-shuttling experiments during the shuttling of the sample from the electron paramagnetic resonance to the nuclear magnetic resonance field. A collection of water proton and protein proton relaxometry profiles, recently obtained in the course of the DNP Design Study project, is here reported, and the relevant parameters are discussed.

Picosecond Coherent Optical Manipulation of a Single Electron Spin in a Quantum Dot

Most schemes for quantum information processing require fast single-qubit operations. For spin-based qubits, this involves performing arbitrary coherent rotations of the spin state on time scales much faster than the spin coherence time. By applying off-resonant, picosecond-scale optical pulses, we demonstrated the coherent rotation of a single electron spin through arbitrary angles up to pi radians. We directly observed this spin manipulation using time-resolved Kerr rotation spectroscopy and found that the results are well described by a model that includes the electronnuclear spin interaction. Measurements of the spin rotation as a function of laser detuning and intensity confirmed that the optical Stark effect is the operative mechanism.

31P magic angle spinning NMR spectroscopy of paramagnetic rare-earth-substituted Keggin and Wells-Dawson solids.

Paramagnetic rare-earth elements have been examined as NMR structural probes in polyoxoanionic solids, which have a variety of applications as luminescent materials that are usually disordered and therefore intractable by traditional structural methods. Thirteen Keggin and Wells-Dawson polyoxotungstates containing substitutions with lanthanides of different effective magnetic moments have been examined by 31P magic angle spinning NMR spectroscopy. The electron-nuclear dipolar interaction dominating the spinning sideband envelopes is determined by the lanthanide's magnetic moment and was found to be a sensitive probe of the nature of the polyoxoanion, of the positional isomerism, and of the ion stoichiometry. Electron-nuclear dipolar anisotropies computed based on the point-dipole approximation are generally in good agreement with the experimental results. The choice of a specific lanthanide as a structural probe can be tailored to the desired distance range between the phosphorus atoms and the paramagnetic centers to be probed. This approach is expected to be particularly useful in the paramagnetic polyoxoanionic materials lacking long-range order.

High resolution EPR spectroscopy of C60F and C70F in solid argon: Reassignment of C70F regioisomers

Free radicals C(60)F and C(70)F were generated in solid argon by means of chemical reaction of photogenerated fluorine atoms with isolated fullerene molecules (C(60) or C(70)). High resolution anisotropic electron paramagnetic resonance (EPR) spectra of C(60)F and C(70)F at low temperature have been obtained for the first time. The spectrum of C(60)F is characterized by an axially symmetric hyperfine interaction on (19)F nucleus. The hyperfine coupling constants A(iso)=202.8 MHz (Fermi contact interaction) and A(dip)=51.8 MHz (electron-nuclear magnetic-dipole interaction) have been measured for C(60)F in solid argon. Quantum chemical calculations using hybrid density-functional models (either PBE0 or B3LYP) with high-quality basis sets give a theoretical estimate of the hyperfine coupling constants in good agreement with the measurements. The electron spin density distribution in C(60)F is theoretically characterized using the Hirshfeld atomic partitioning scheme. Unlike C(60), five isomers of C(70)F can in principle be produced by the attachment of a fluorine atom to one of the five distinct carbon atoms of the C(70) molecule (denoted A, B, C, D, and E, from pole to equator). The measured high resolution EPR spectrum of the C(70)+F reaction products is interpreted to show the presence of only three regioisomers of C(70)F. Based on the comparison of the measured hyperfine constants with those estimated by the quantum chemical calculation, an assignment of the spectra to the isomers (A, C, and D) is made, which differs strongly from the previous one [J. R. Morton, K. F. Preston, and F. Negri, Chem. Phys. Lett. 221, 59 (1994)]. The new assignment would allow the conclusion that the low-temperature attachment of F atom to the asymmetric C=C bonds of C(70) molecule, namely, C(A)[Double Bond]C(B) and C(D)=C(E), shows remarkably high selectivity, producing only one of the two isomers in each case, A and D, respectively. Theoretical investigation of the reaction mechanism is made, and it shows that the attachment reaction should have no barrier in the gas phase. The thermodynamic equilibration of the C(70)F isomers is excluded by the high activation energy ( approximately 30 kcal/mol) for the F atom shifts. The explanation of the high selectivity presents a challenge for theoretical modeling.

Nuclear Spin Ferromagnetic Phase Transition in an Interacting Two Dimensional Electron Gas

Electrons in a two-dimensional semiconducting heterostructure interact with nuclear spins via the hyperfine interaction. Using a a Kondo lattice formulation of the electron-nuclear-spin interaction, we show that the nuclear-spin system within an interacting two-dimensional electron gas undergoes a ferromagnetic phase transition at finite temperatures. We find that electron-electron interactions and non-Fermi liquid behavior substantially enhance the nuclear-spin Curie temperature into the mK range with decreasing electron density.

Dynamical nuclear spin polarization and the Zamboni effect in gated double quantum dots

A dynamical nuclear polarization scheme is studied in gated double dots. We demonstrate that a small polarization $(\ensuremath{\sim}0.5%)$ is sufficient to enhance the singlet decay time by two orders of magnitude. This enhancement is attributed to an equilibration process between the nuclear reservoirs in the two dots accompanied by reduced fluctuations in the Overhauser fields that are mediated by the electron-nuclear spin hyperfine interaction.

First principles study of nuclear quadrupole interactions in the molecular solid BF3 and the nature of binding between the molecules

The electronic structures and nuclear quadrupole interactions (NQI) of the 19F* (I= 5/2) state of 19p nucleus in solid BP3 are studied using the first-principles Hartree-Fock-Roothaan procedure including many-body electron correlation effects. The calculated NQI parameters, 19p* quadrupole coupling constant (e2qQ) and asymmetry parameter η,were found to be in satisfactory agreement with experiment for the solid state system, which gives confidence in the reliability of the calculated electronic structures in the solid and hence the factors found to influence the binding of the molecules in the solid. It was found that the intermolecular binding energy primarily arises from Van der Waals (VDW) interactions between the molecules resulting from intermolecular many-body effects, which counteract the repulsive interactions between the molecules arising from one-electron Hartree-Fock (HP) theory.

Theory of electronic structure and nuclear quadrupole interactions in the BF3–NH3 complex and methyl derivatives

Magnetic Hyperfine and Nuclear Quadrupole Interactions (HPI and NQI) are now important tools for characterization of systems of interest in materials research and industry. Boron-Trifluoride is an inorganic compound that is very important in this respect as a catalyst in chemical physics research and industry, forming complexes in the process with compounds like ammonia, water and methyl alcohol. The present paper deals with the BP3-NH3 complex and methyl derivatives BP3NHx(CH3)3-x for which we have studied the electronic structures, binding energies, and 19F* (I=5/2) nuclear quadrupole interactions using the first-principles Hartree-Fock-Roothaan procedure combined with electron correlation effects. Our results for the 19F* nuclear quadrupole coupling constant (e 2qQ/h) in units of MHz compare well with experiment. Trends in the binding energies and NQI parameters between the complexes are discussed.

Subsecond Spin Relaxation Times in Quantum Dots at Zero Applied Magnetic Field Due to a Strong Electron-Nuclear Interaction

A key to ultralong electron spin memory in quantum dots (QDs) at zero magnetic field is the polarization of the nuclei, such that the electron spin is stabilized along the average nuclear magnetic field. We demonstrate that spin-polarized electrons in n-doped (In,Ga)As/GaAs QDs align the nuclear field via the hyperfine interaction. A feedback onto the electrons occurs, leading to stabilization of their polarization due to formation of a nuclear spin polaron [I. A. Merkulov, Phys. Solid State 40, 930 (1998)]. Spin depolarization of both systems is consequently greatly reduced, and spin memory of the coupled electron-nuclear spin system is retained over 0.3 sec at temperature of 2 K.

Responsive fluorinated lanthanide probes for 19F magnetic resonance spectroscopy

The introduction of CF(3) reporter groups close to the paramagnetic centre in macrocyclic lanthanide(iii) complexes allows faster acquisition of (19)F magnetic resonance data, and amplifies chemical shift non-equivalence, as exemplified by the definition of ratiometric chemical shift probes for pH and, in principle, enzyme activity.

Probing Local Environments in Paramagnetic Europium-Substituted Keggin Solids by 31P Magic Angle Spinning NMR Spectroscopy

Paramagnetic Eu-substituted Keggin oxopolytungstates crystallize in different forms, determined by the nature of the counterions. The crystal packing is in turn responsible for the variations in the geometry of paramagnetic Eu sites with respect to the anion core. We probed the paramagnetic environments in a series of Eu-substituted Keggin solids, by 31P magic angle spinning NMR spectroscopy. 31P spinning sideband envelopes are dominated by the electron-nuclear dipolar interaction. For the compounds under investigation, both the magnitude and the asymmetry parameter of the electron-nuclear dipolar coupling tensor are sensitive to the mutual arrangements of paramagnetic Eu sites in the crystal lattice. and also report on the stoichiometry of the anion. The electron-nuclear dipolar coupling tensors were calculated from the crystallographic coordinates and the experimentally determined effective magnetic moments, assuming a point dipole approximation. The computed tensors are in very good agreement with the experimental spectra. Furthermore, the P-Eu distance estimates, accurate to within 0.06-0.12 A, can be obtained directly from the magnitude of the electron-nuclear dipolar coupling. This work demonstrates that 31P MAS NMR spectroscopy is a useful probe for investigating local environments in paramagnetic Keggin solids.