Satellite structure of DNP enhanced 13C NMR spectra in diamond

The P1 nitrogen defect centres in natural type Ia diamonds have been exploited in dynamic nuclear polarization (DNP) of the ¹³C nuclei (1.1% abundant) via the solid-effect. We have achieved sufficiently large ¹³C polarizations in some diamonds to observe weak satellite lines in the ¹³C NMR spectra by using long microwave irradiation times. A study of the dependence of the NMR spectra on the crystal orientation with respect to the applied magnetic field reveals that the satellite structure originates from the small fraction of ¹³C nuclei that are involved in nearest neighbour dipole interactions. This revised version was published online in August 2006 with corrections to the Cover Date.     

A novel use of hyperfine structure in the electron paramagnetic resonance of interacting pairs of paramagnetic defects in diamond

It is the hyperfine structure of ¹⁴N and ¹³C in the electron paramagnetic resonance (EPR) spectrum which indicates that the unpaired electron of a single substitutional nitrogen atom in diamond is in one of the four anti-bonding N-C orbitals. We show that, for diamonds containing a very high concentration of nitrogen, the hyperfine structure of interacting pairs of nitrogen atoms indicates that for close neighbours there are unique orientations of the constituent N-C bonds, while at larger distances the orientations are random. This revised version was published online in August 2006 with corrections to the Cover Date.     

14N fusion with 13C and 16O at sub-barrier energies

Total fusion cross sections for the ¹⁴N+¹²C and ¹⁴N+¹⁶O reactions have been measured in the c.m. energy ranges 3.6–9.2 MeV and 5.6–12.6 MeV, respectively. Cross sections are also reported for important individual exit channels which were studied by observing discrete γ-ray transitions in the evaporation residues with a Ge(Li) detector. Excitation functions reveal no evidence of intermediate structure in these reactions. The fusion cross sections for ¹⁴N induced reactions on ¹²C, ¹⁴N and ¹⁶O are compared with an IWB calculation using recently published semi-empirical parameters for the real ion-ion interaction potential. Such a comparison supports the view that low-energy fusion studies may be sensitive probes of the nuclear potential in the interior of the interaction barrier.     

13C hyperfine splitting in the benzene negative ion

A method is developed to calculate the coefficients appearing in the Høye, Stell and Waisman analytic solution of the Ornstein-Zernike equation for a hard core potential with a direct correlation function of the two Yukawa form. The method is simple and makes the choice of a physical solution easy. The compressibility, energy and virial pressures are calculated in the vicinity of the liquid-gas transition region and their dependence on changing K ₂, the amplitude of the repulsive Yukawa part, is analysed. This method offers promising possibilities for the application of the hard core, two Yukawa (HCTY) system in the theory of fluids.     

The role of point defects in melting of solid He

We have recently observed that the resistance to shear of solid ⁴He decreases dramatically near the first-order BCC–HCP transition. In our view, the solid shears via a diffusive counter-flow of atoms and point defects. The mechanism of self diffusion couples point defects with one specific phonon which softens as the transition is approached. Since such a scenario can possibly lead to melting, it is important to understand (a) which type of point defect is associated with the reduction of shear resistance, and (b) can the presence of point defects lead to the softening of phonons. We report here the results of numerical simulations and analytic modeling. Our results indicate that split interstitials are much more effective than vacancies in lowering the resistance to shear. We suggest that these excitations can be generated as a result of a “local mode” excited in the crystal.     

Obtaining molecular and structural information from 13C-14N systems with 13C FIREMAT experiments

The effect of dipolar coupling to 14N on 13C FIREMAT (five pi replicated magic angle turning) experiments is investigated. A method is developed for fitting the 13C FIREMAT FID employing the full theory to extract the 13C-14N dipolar and 13C chemical shift tensor information. The analysis requires prior knowledge of the electric field gradient (EFG) tensor at the 14N nucleus. In order to validate the method the analysis is done for the amino acids alpha-glycine, gamma-glycine, l-alanine, l-asparagine, and l-histidine on FIREMAT FIDs recorded at 13C frequencies of 50 and 100 MHz. The dipolar and chemical shift data obtained with this analysis are in very good agreement with the previous single-crystal 13C NMR results and neutron diffraction data on alpha-glycine, l-alanine, and l-asparagine. The values for gamma-glycine and l-histidine obtained with this new method are reported for the first time. The uncertainties in the EFG tensor on the resultant 13C chemical shift and dipolar tensor values are assessed.     

Double-quantum solid-state NMR of 13C spin pairs coupled to 14N

We examine the double-quantum magic angle spinning NMR spectra of pairs of 13C nuclei coupled to one or more 14N nuclei. The experimental spectra of 13C(2)-glycine and glycyl-[13C(2)]-glycyl-glycine are used to demonstrate the sensitivity of the spectra to the orientation of 14N quadrupole interaction tensors and to the molecular torsional angles.     

First principles cluster investigation of electronic structure and hyperfine interaction for nitrogen in diamond

The self-consistent field Unrestricted Hartree-Fock cluster procedure has been used to study the location, electronic structure and hyperfine properties of nitrogen impurity in diamond. From the analysis of the potential energy curve for nitrogen along the <111> axis, it was found that nitrogen is located at a position 0.3A away from the substitutional site towards the plane formed by the three nearest neighbour carbon atoms. The calculated values of the magnetic hyperfine constants and nuclear quadrupole coupling constants for¹⁴N agree very well with values obtained from electron paramagnetic resonance and electronnuclear double resonance measurements.     

Decoupling residual dipolar coupling between 13C and14N spin pairs in CPMAS NMR

Decoupling of the residual dipolar coupling between ¹³C and¹⁴N nuclei is investigated experimentally in a triple resonance experiment. It is shown that pulsed decoupling can be used to give enhanced sensitivity and reduced line widths and the technique is illustrated using short peptides.     

The use of ENDOR to identify the atomic structure of defects in diamond

Although nearly 100 paramagnetic defects have been catalogued in diamond by spin Hamiltonian parameters measured by electron paramagnetic resonance (EPR), very few of these have been unambiguously associated with an atomic model. It has been necessary to use electron nuclear double resonance (ENDOR) to obtain enough information to make proper assignment of such models. The reason for the limitation of EPR, and the way in which ENDOR overcomes these limitations are discussed. The interpretation of hyperfine structure in terms of unpaired electrons in molecular orbitals, and of quadrupole interactions in terms of all electrons, paired and unpaired, as a source of information about molecular structure in diamond, is evaluated by reference to some well documented examples. The measurements so far made by ENDOR on defects in diamond are reviewed, and the salient contribution for the assignment of a model for each defect is explained. The details revealed by ENDOR considerably increase knowledge about defects, particularly those involving substitutional nitrogen atoms. This in turn helps in understanding the complex electron and atom, migration processes which go on under appropriate conditions of temperature and pressure, or optical excitation. The possibilities are discussed for using ENDOR to increase the number of well characterized centres.     

The role of the 14N(n,p)14C reaction in neutron irradiation of soft tissues

The cell-killing potential of the ¹⁴N(n,p)¹⁴C reaction was considered with regard to neutron absorption in human nuclear DNA and respiratory phosphates for: (A) 10¹² thermal neutrons in 1 kg of soft tissue, (B) a mono-energetic beam of 2 MeV neutrons incident in 1 kg of soft tissue such that the total collision kerma was 10 J/kg, and (C) an evenly distributed 0–66 MeV neutron beam, also incident in 1 kg such that the total collision kerma was 20 J/kg. For case (A) 0.0017 ¹⁴N(n,p)¹⁴C reactions could be expected per DNA double strand, case (B) 0.053, and case (C) 0.0039. The probabilities that a proton emitted outside the nucleus would cross nuclear DNA were estimated from ¹⁴N tissue content for adult skeletal muscle, liver, and kidney tissues, for (1) nuclear DNA being concentrated in a sphere of 1.8 μm diameter, and (2) nuclear DNA being evenly distributed in a spherical nucleus 5 μm in diameter. It was concluded that even in a nitrogen-rich tissue exposed to a collision kerma of 20 J/kg by a 0–66 MeV fast neutron beam, the ¹⁴N(n,p)¹⁴C reaction directly kills at most 10 cells in every 1000, 4 of these by DNA nitrogen absorption and 6 by the ¹⁴N(n,p)¹⁴C protons emitted elsewhere in the cell. However, the dose due to the ¹⁴N(n,p)¹⁴C reaction should be measured where exposure to thermal neutron fluxes is significant. For therapeutic neutron doses the number of respiratory phosphate molecules in which the ¹⁴N(n,p)¹⁴C reaction occurs is insignificant, and doses from ¹⁴C-decay after neutron therapy are also negligible.     

Decoupling residual dipolar coupling between 13C and14N spin pairs in CPMAS NMR

Decoupling of the residual dipolar coupling between ¹³C and¹⁴N nuclei is investigated experimentally in a triple resonance experiment. It is shown that pulsed decoupling can be used to give enhanced sensitivity and reduced line widths and the technique is illustrated using short peptides.     

Stretched M4 configurations in 14C and 14N

Shell model results for the form factors for electro-excitation to stretched M4 configurations in ¹⁴C and ¹⁴N are confronted with recent data. Estimates for the partial nucleon emission channels of prominent isovector M4 resonances are presented.     

The hyperfine structure and hyperfine anomaly of 161Dy and 163Dy

The hyperfine structure of ¹⁶¹Dy and ¹⁶³Dy for five transitions hasbeen measured with a tunable dye laser and a thermal velocity atomic beam. Values for the magnetic dipole and electric quadrupole coupling constants have been determined for the relevant excited states. The hyperfine anomaly parameters, Δ, which are extracted are interpreted in terms of available atomic wave functions.     

Study of spin-orbit interaction of13C and15N nuclei in14C induced transfer reactions on138Ba

Angular distributions of single nucleon transfer reactions populating single particle states in the reactions¹³⁸Ba(¹⁵C,¹⁴N)¹³⁷Cs and¹³⁸Ba(¹⁴C,¹³C)¹³⁹Ba have been studied. The shapes of the angular distributions show differences for different final configurations. Using the reaction asymmetry it is possible to describe these differences consistently for all transitions by a spin-orbit potential. The polarisation of the outgoing fragments is discussed and its dependence on final configurations is explained. The spin-orbit potentials deduced from the reaction asymmetry are large, as compared to predictions of folding potentials. They are, however, consistent with measurements of spin-flip probabilities. The origin of theL-S interaction is to be found in coupling effects of second order in the heavy ion reaction.