A deuteron NMR study of axial motion and side chain conformation in the mesophase of discotic liquid crystal main-chain polymers

Pulsed deuteron NMR spectroscopy has been used to examine the axial motion and the side-chain conformation in both oriented and unoriented mesophases of discotic liquid crystal main-chain polymers based on pentyloxy or heptyloxy substituted triphenylenes. Lineshape simulations show that the rotational motion of the triphenylene rings about the column axes can be described by an inhomogeneous distribution of reorientation angles around 45°. However, only about 60% of the discs are involved in such large amplitude motions; the remaining 40% have reorientation angles below 10°. This illustrates the severe restrictions imposed on the rotation of the discs by the interlinkage of the columns via the alkylene spacers. Furthermore, the simulations demonstrate that, at the -carbon, the side chains show very little fast internal motion, but have a relatively complex conformation involving a disorder which does not change on the microsecond timescale. Since such a disorder is not present in the corresponding monomeric samples it is ascribed to the presence of the spacers. These results are also consistent with the presence of large sterical hindrances between the first side chains segments of adjacent discs, and they indicate a correlated reorientation of the discotic units within a column.     

基于散射实验极化靶的2.5T/1.3K的动态核极化(DNP)系统的开发

动态核极化法(Dynamic Nuclear Polarization, DNP)是利用热平衡下的电子在磁场中的高自旋极化率转移到原子核自旋的技术,从而极大的提高原子核自旋极化率。多种动态极化靶材料已广泛的用于自旋物理散射实验。本文介绍一种简单实用,共同开发的日本山形大学DNP系统,包括超导磁场,氦4蒸发恒冷器,微波系统以及NMR核磁共振检测系统,测得中子靶材料氘带丁醇(D-butanol)中氘核的极化率在2.5T/1.3K达到+6.5%。     

Deuteron NMR spectra of ammonium ion isotopomers at low temperatures

Partially deuterated ammonium compounds contain ammonium ion isotopomers with relative abundances given by the binomial distribution of protons and deuterons. All isotopomers with deuterons contribute characteristic deuteron NMR spectra at 5K. Experimental NMR spectra were separated and respective contributions of isotopomers were determined. The derived contributions agree with expected values for a given deuteration in the case of ammonium hexafluorophosphate. In ammonium hexachlorotellurate both NH2D2+ and about 50% of NH3D+ ions are rigid, while the remaining NH3D+ perform limited jumps. NHD3+ and ND4+ ions undergo tunnelling rotation, NH3D+ ions perform either jumps about C2 axis or limited jumps, but some stay rigid in ammonium hexachlorostannate. NH2D2+, NHD 3+ and ND4+ undergo rotational tunnelling. In the case of ammonium perchlorate, the NH3D+ ions perform either jumps about C3 axis or limited jumps whilst some remain rigid. Very low values of activation energies were derived for all spectral components from the temperature dependence of their spectra, up to about 20K, which indicates an incoherent tunnelling nature of the observed dynamic processes. The diverse mobility of NH3D+ ions appears to be the most interesting and new feature.     

Incoherent pion photoproduction on the deuteron including polarization effects

Incoherent pion photoproduction on the deuteron including polarization effects is studied in the energy region from π-threshold up to the Δ(1232)-resonance with inclusion of all leading πNN effects. For the elementary pion photoproduction operator, a realistic effective Lagrangian approach is used which displays chiral symmetry, gauge invariance, and crossing symmetry, as well as a consistent treatment of the spin-3/2 interaction. The interactions in the final two-body subsystems are taken in separable form. Effects of final state interaction are investigated and their role in unpolarized and polarization observables are found to be significant. The extracted cross sections and spin asymmetries are compared with available experimental data and predictions of other works, and a satisfactory agreement is obtained. In addition, the sensitivity of results to the elementary N(γ, π)N operator is investigated. Considerable dependence of the d(γ, π)NN results on the elementary amplitude is found. This indicates that it can serve as a filter for different elementary operators.     

Deuteron size effects on its elastic scattering from1H and4He

The effect of change in deuteron size on its elastic scattering from protons and alphas is investigated by varying the Hulthen parameters of the deuteron wave function in the scattering process. The cross sections forp-d scattering, calculated in the Born approximation, are found to increase substantially at backward angles even when the deuteron size is reduced by a small amount, whereas the shape of the angular distribution does not change significantly. For theα-d elastic scattering, interaction potential is obtained by folding the deuteron wave function and the optical potential for nucleon-scattering. The cross sections calculated atE _d = 13·7 MeV, shows that the first minimum around Θ_cm = 60° is deepend as the deuteron size is reduced, while at 52 MeV bombarding energy, the size effects are not very distinct. These observations are useful in the interpretation of deuteron cluster knockout reactions.     

Deuteron NMR spin–lattice relaxation of NH3D ions in partially deuterated (NH4)2SnCl6 and NH4ClO4

Deuteron spin–lattice relaxation is studied in 5% and 100% deuterated ammonium hexachlorostannate and perchlorate. The relaxation rate is observed to be independent of deuteration down to temperatures slightly lower than that of the maximum. At lower temperatures the rate of the 5% deuterated sample exceeds that of the 100% deuterated sample by four and two orders of magnitude in ammonium hexachlorostannate and perchlorate, respectively. The angular dependence of the deuteron relaxation rate in 5% deuterated ammonium hexachlorostannate at 6 K is explained in terms of existing models on quadrupolar relaxation. In 5% ammonium perchlorate one hydrogen equilibrium position, which lies on the preferred axis for 120° rotations, has a larger probability to be occupied by the deuteron of NH₃D⁺ ions. The deuterons at the other positions are still performing rotational jumps about the preferred C₃ axis and also about the other threefold axes, although at a slower rate. Such observations require a reconsideration of the relaxation process. A somewhat more general expression is derived for the relaxation rate, which agrees with the experimentally observed angular dependence for 5% deuterated ammonium perchlorate at 60 K. At lower temperatures the quadrupole coupling of the deuterons at the preferred axis may become practically time-independent. Then a significant contribution to the relaxation rate can be provided by the deuteron–proton magnetic dipolar interaction, which is still fluctuating fast via the rotation of the three protons about the axis through the stationary deuteron.     

Anomalous heat evolution of deuteron implanted al upon electron bombardment III - try to observe the nuclear d-d reaction

In previous papers, one of the authors (K. K.) has observed the anomalous melting of the surface layer of deuteron implanted Al, containing so-called "tunnel structures", on the electron bombardment in transmission electron microscope. In the present paper, we intended to observe the evidence of the d-d nuclear reaction, expecting neutron emission, associated with the melting phenomenon. However, the result was rather unexpected. The melting phenomenon was certainly observed under the same experimental conditions as before. But, in spite of the melting, neutron emission associated with the nuclear reaction was not observed. And, more unexpectedly, X-ray emission of energy less than roughly 400 v keV was observed when specimens with a bubble structure, which never showed melting, were bombarded with electron beams. Several conceivable mechanisms are discussed which, however, are all not convincing to explain the melting. The melting is attributed to some excess energy generation. The error estimation of the radiation measurements was undertaken.     

Parity nonconservation in the deuteron photodisintegration

We calculate P-odd difference of the total cross sections of the deuteron disintegration by left and right polarized photons. The relative magnitude of this difference in the threshold region is about 10⁻⁷. Its experimental measurement would give valuable information on the weak nucleon–nucleon interaction at short distances.     

Chain dynamics in a chiral C phase by deuteron spin relaxation study

Molecular reorientations and internal conformational transitions of an aligned chiral liquid crystal (LC) 10B1M7 are studied by means of deuterium spin-lattice relaxation in its smectic A (SmA) and smectic C* (SmC*) phase. The motional model which is applicable to uniaxial phases of many LCs is found to be adequate even when the phase is a tilted SmC* phase. The deuterium NMR spectrum in this phase cannot discern rotations of the molecular director about the pitch axis. The basic assumption is that the phase biaxiality is practically unobservable. However, the relaxation rates can be accounted for by the tilt angle between the molecular director and the layer normal in the SmC* phase. The tumbling motion appears to show a higher activation energy upon entering from the uniaxial SmA into the SmC* phase.     

Bond orbital analysis of the deuteron quadrupole coupling constants in MD4 molecules

The deuteron quadrupole coupling constants were used as constraints on the bond orbital functions of a series of MD₄ molecules (M=B, C, N, Al, Si, P). It was demonstrated that a minimal basis set may be sufficient to describe first row deuterates, but not for second row deuterates, where double zeta orbitals are needed.This work was started when the author was a post doctoral fellow at Battelle Memorial Institute, Columbus, Ohio.