Quantum state of muon and proton in crystalline silicon

Quantum state and dynamics of muon and proton in crystalline silicon have been studied by solving one‐particle Schrödinger equations for the impurities. The ground state wavefunctions and energies are determined as a function of local distortion of the host Si lattice, where the Si–H interaction we used is that parameterized by Ramírez and Herrero following the results of earlier pseudopotential‐density‐functional calculation. It is shown that quantum zero‐point motion of muon induces an effective potential barrier between the tetrahedral‐symmetry (T) site and the bond‐center (BC) site, which ensures bistability of muonium states observed in experiments. It is also shown that, if we fully consider the quantum effect with the present model potential, the BC site becomes less stable than the T site on the contrary to the experiments and former theoretical calculations.     

Determination of NMR interaction parameters from double rotation NMR

It is shown that the anisotropic NMR parameters for half-integer quadrupolar nuclei can be determined using double rotation (DOR) NMR at a single magnetic field with comparable accuracy to multi-field static and MAS experiments. The (17)O nuclei in isotopically enriched l-alanine and OPPh(3) are used as illustrations. The anisotropic NMR parameters are obtained from spectral simulation of the DOR spinning sideband intensities using a computer program written with the GAMMA spin-simulation libraries. Contributions due to the quadrupolar interaction, chemical shift anisotropy, dipolar coupling and J coupling are included in the simulations. In l-alanine the oxygen chemical shift span is 455 +/- 20 ppm and 350 +/- 20 ppm for the O1 and O2 sites, respectively, and the Euler angles are determined to an accuracy of +/- 5-10 degrees . For cases where effects due to heteronuclear J and dipolar coupling are observed, it is possible to determine the angle between the internuclear vector and the principal axis of the electric field gradient (EFG). Thus, the orientation of the major components of both the EFG and chemical shift tensors (i.e., V(33) and delta(33)) in the molecular frame may be obtained from the relative intensity of the split DOR peaks. For OPPh(3) the principal axis of the (17)O EFG is found to be close to the O-P bond, and the (17)O-(31)P one-bond J coupling ((1)J(OP)=161 +/- 2 Hz) is determined to a much higher accuracy than previously.     

Solid state NMR study of nanodiamond surface chemistry

Solid state NMR measurements using 13C, 1H and 19F nuclei (MAS, CP-MAS) underline the surface chemistry of nanodiamonds from different synthesis (detonation, high pressure high temperature and shock compression). The comparison of the spin-lattice relaxation times T1 and physicochemical characterization (spin densities of dangling bonds, specific surface area and Raman and infrared spectroscopies) for the various samples, as synthesized, chemically purified and fluorinated allows the nature and the location of the various groups, mainly C-OH, C-H and C-F to be investigated. C-OH groups are located only on the surface whereas C-H and dangling bonds seem to be distributed in the whole volume. Fluorination was studied as a chemical treatment for purification and change of the hydrophobicity through the conversion of the C-OH groups into covalent C-F bonds.     

Solid state 33S NMR of inorganic sulfides

Solid state 33S NMR spectra of a variety of inorganic sulfides have been obtained at magnetic field strengths of 4.7 and 17.6T. Spectra acquired with magic angle spinning show considerable improvements in sensitivity and resolution when compared with static spectra. Multiple factors are considered when analyzing the spectral line widths, including; magnetic field inhomogeneity, dipolar coupling, chemical shift anisotropy, chemical shift dispersion (CSD), T(2) relaxation, and quadrupolar coupling. Quadrupolar coupling was expected to be the dominant line broadening mechanism. However, for most of the samples CSD was the prevailing line broadening mechanism. Thus, for many of the metal sulfides studied at a high magnetic field strength, the line widths were actually larger than those observed in the spectra at low field. This is atypical in solid state 33S NMR. Solid state 33S spin-lattice (T(1)) and spin-spin (T(2)) relaxation rates were measured for the first time and are discussed. This information will be useful in future efforts to use 33S NMR in the compositional and structural analysis of sulfur containing materials.     

Solid state 19F NMR parameters of fluorine-labeled amino acids. Part I: aromatic substituents

Structural parameters of peptides and proteins in biomembranes can be directly measured by solid state NMR of selectively labeled amino acids. The 19F nucleus is a promising label to overcome the low sensitivity of 2H, 13C or 15N, and to serve as a background-free reporter group in biological compounds. To make the advantages of solid state 19F NMR fully available for structural studies of polypeptides, we have systematically measured the chemical shift anisotropies and relaxation properties of the most relevant aromatic and aliphatic 19F-labeled amino acids. In this first part of two consecutive contributions, six different 19F-substituents on representative aromatic side chains were characterized as polycrystalline powders by static and MAS experiments. The data are also compared with results on the same amino acids incorporated in synthetic peptides. The spectra show a wide variety of lineshapes, from which the principal values of the CSA tensors were extracted. In addition, temperature-dependent T(1) and T(2) relaxation times were determined by 19F NMR in the solid state, and isotropic chemical shifts and scalar couplings were obtained in solution.     

Solid state 19F NMR parameters of fluorine-labeled amino acids. Part II: aliphatic substituents

A representative set of amino acids with aliphatic 19F-labels has been characterized here, following up our previous compilation of NMR parameters for single 19F-substituents on aromatic side chains. Their isotropic chemical shifts, chemical shift tensor parameters, intra-molecular 19F dipole-dipole couplings and temperature-dependent T1 and T2 relaxation times were determined by solid state NMR on twelve polycrystalline amino acid samples, and the corresponding isotropic 19F chemical shifts and scalar couplings were obtained in solution. Of particular interest are amino acids carrying a trifluoromethyl-group, because not only the 19F chemical shift but also the intra-CF3 homonuclear dipolar coupling can be used for structural studies of 19F-labeled peptides and proteins. The CF3-groups are further compared with CH2F-, CD2F-, and CD3-groups, using both 19F and 2H NMR to describe their motional behavior and to examine the respective linebroadening effects of the protonated and deuterated neighbors. We have also characterized two unnatural amino acids in which a CF3-label is rigidly connected to the backbone by a phenyl or bicyclopentyl moiety, and which are particularly well suited for structure analysis of membrane-bound polypeptides. The 19F NMR parameters of the polycrystalline amino acids are compared with data from the correspondingly labeled side chains in synthetic peptides.     

Solid state effects during deuterium implantation into copper and titanium

Results of neutron counting experiments during deuterium implantation into titanium and copper are reported. Models for neutron yield have been developed by taking into account different solid state effects like energy degradation of incident ions, energy dependent d-d fusion cross section and diffusion of implanted deuterium possibly influenced by surface desorption and formation of metal deuterides. The asymptotic time dependence of the neutron yield during implantation has been compared with the experimental results. Using these results, solid state processes that might occur during deuterium implantation into these metals are inferred.     

NMR study of the motion of oxygens in some oxysalts

The temperature dependence of the proton spin-lattice relaxation times T₁ and T_1? were measured in some partially deuterated ammonium compounds; ammonium perchlorate and ammonium dichromate. The extremely large minimum values of T_1? (2 ～ 3 sec) were found to be independent of the concentration of deuterons. These minima of T_1? were attributed to the random modulation of the dipolar interaction between the protons and ¹⁷O (0.037%) of low abundance. The activation energy E_a of the reorientation of ClO₄ and CrO₃ were determined to be 6.2 and 10.7 kcal mol^-1, respectively.     

Solid state NMR free induction decay in the presence of vacancy diffusion

A theoretical calculation of the NMR free induction decay (FID) of spins in a periodic lattice is given where the spin-spin interaction is dipolar and where account is taken of vacancy motion. The expansion of the FID to any order is exact which allows for the inclusion of effects arising from nearest neighbor and next nearest neighbor (τ_NN and τ_NNN) hopping times. It is shown that expansion of the FID to terms of order t⁴ allows for the separate determination of τ_NN and τ_NNN.     

Solid state NMR study of carbon bonding in amorphous hydrogenated carbon films

Carbon bonding environments in hydrogenated amorphous carbon films (a-C:H) deposited from an rf-biased methane plasma onto various substrates have been quantified by application of solid state¹³C NMR. A family of films were prepared by systematically varying the substrate bias voltage. Quantitative data on carbon chemistry in these films is required for modeling the impact of structure on mechanical and optical properties. A variety of NMR acquisition pulse sequences have been investigated to determine the conditions under which quantitative¹³C NMR data can be acquired in this system. The results indicate that data acquisition from this material requires different protocols than for the study of polymeric hydrocarbon films. With proper experimental design, NMR is an excellent technique for structural studies of these materials.     

Solid phase formation of silicon nanocrystals by bulk ultrafast laser-matter interaction

Ultrashort pulse laser interaction with silica-silicon interfaces is presented as a means for all-solid-phase formation of high-purity silicon nanoparticles in the absence of ablation plumes or any substrate intermixing with surfaces in ambient air. Transmission electron microscopy and Raman spectroscopy provide definitive evidence for creation of nanocrystals in the silica host, while compressive stress in the silicon substrate corroborates the formation of optical waveguides parallel to the tracks.     

Solid state NMR characterisation of the thermal transformation of Fuller''s Earth

Fuller's Earth, a dioctahedral calcium montmorillonite clay mineral of the smectite group, undergoes thermal transformation via a series of complex intermediate states that are highly structurally disordered. Fuller's Earth is a commercially significant material with considerable levels of paramagnetic iron (Fe³⁺) substitution into octahedrally coordinated metal sites. Despite the high iron-content (˜ 10% of the occupied octahedral metal sites) in these samples ²⁹Si and ²⁷Al magic angle spinning (MAS) NMR spectra of sufficient quality are obtained to reveal structural changes in samples that have been heated from room temperature to 1400 °C. Two major structural changes are clearly observed, initial dehydroxylation and then collapse of the layer structure into more highly connected silica-rich domains and an alumina-rich phase.     

States of hydrogen in crystalline silicon

The thermal transformation of deuterium in p-type crystalline silicon is studied with a variety of experimental techniques. It is found that D-atoms initially trapped at acceptor sites can be transferred by low temperature annealing to a different state tentatively ascribed to interstitial D₂ molecules. Diffusion of D out of the passivated sample only occurs at temperatures significantly higher than this transformation temperature. This fact allows us to produce Si samples with extremely high deuterium concentrations (several at%) by a suitable passivation-annealing sequence. With increasing D-concentration, a number of characteristic Si-D defect complexes have been observed by vibrational spectroscopy.     

Hydrogen in phosphorus- and carbon-doped crystalline silicon

The formation kinetics of the H-C complex in P-doped silicon have been studied using the DLTS and C-V profiling methods. The measurements show that the hydrogen species that is incorporated in the H-C complex originates from H-P complexes which act as a “hydrogen reservoir”. The dissociation energy of the H-P complexes is determined to be 1.13 eV. The results of C-V measurements clearly indicate that there exists a negatively charged H-species after the dissociation of the H-P complexes. H motion in an electric field seems to occur via a “hopping mechanism”.