Induced smectic C* phases

Induced ferroelectric S*_C phases are formed by non-chiral S_C host phases doped with chiral dipolar guest molecules. In those mixtures the spontaneous polarization P_s and the tilt angle Θ has been investigated as a function of the mole fraction x_G of the chiral dopant. In most cases the reduced polarization P₀ = P_S/ sin Θ has been found to depend linearly on x_G. The polarization power which is defined by δ_P=(∂P₀/∂x_G)ΔT is discussed in terms of the molecular structure of the chiral dopants. There are systems in which P₀(x_G) deviates positively from linearity. This behaviour can be understood by considering a local field correction to P₀. By assuming a local field of Lorentz type a theoretical relation for P₀(x_G) has been derived which explains the experimental results. The effect of a local field is considerable if the transverse dipole moment and the polarizability of the chiral dopant are large.     

Lipid chain mobility in interdigitated DPPC systems

The segmental lipid chain mobility in the gel phase of dipalmitoylphosphatidylcholine (DPPC) multilayers dispersed in buffer and in the interdigitated gel phase induced by glycerol, ethylene glycol, ethanol and chaotropic salt NaClO₄ was compared by using conventional electron spin resonance (ESR) spectroscopy. The stearic acids bearing the nitroxide moiety at different positions down the acyl chain (n-NSA,n-5, 7, 10, 12 and 16) were used to characterized the chain motion, and the outer hyperfine splittings of the spectra, 2A _max, were taken as indices of the rotational mobility of the chain in the gel phase. The ESR measurements revealed a gradient of increased mobility on proceeding towards the terminal methyl end in the fully hydrated gel phase of DPPC bilayers. This gradient was reduced in the interdigitated gel phase induced by ethanol and chaotropic salt NaClO₄, whereas the rotational mobility throughout the length of the chain was comparable to that near the polar/apolar interface in the interdigitated gel phase in glycerol and ethylene glycol. Moreover, the motional anisotropy was much less affected by temperature in the interdigitated gel state of DPPC in glycerol and ethylene glycol as compared both to normal bilayer gel phase and to the other interdigitated DPPC systems. Finally, there was no evidence for chain interdigitation in the fluid phase of DPPC dispersions in any medium.     

COSMIC(90): An improved molecular mechanics treatment of hydrocarbons and conjugated systems

Summary Four modifications to the COSMIC molecular mechanics force field are described, which greatly increase both its versatility and the accuracy of calculated conformational energies. The Hill non-bonded van der Waals potential function has been replaced by a two-parameter Morse curve and a new H-H potential, similar to that in MM3, incorporated. Hydrocarbon energies in particular are much improved.A simple iterative Hückel pi-electron molecular orbital calculation allows modelling of conjugated systems. Calculated bond lengths and rotational barriers for a series of conjugated hydrocarbons and nitrogen heterocycles are shown to be as accurate as those determined by the MM2 SCF method.Explicit hydrogen-bonding potentials for H-bond acceptor-donor atom pairs have been included to give better hydrogen bond energies and lengths. The van der Waals radii of protonic hydrogens are reduced to 0.5 Å and the energy well depth is increased to 1.0 kcal mol^-1.Two new general atom types, N⁺ _sp ² and O^- _sp ³ , have been introduced which allow a wide variety of charged conjugated systems to be studied. A minimum of parameterisation is required, as the new types are easily included in the Hückel scheme which automatically adjusts bond and torsional parameters according to the defined bond-order relationships.     

Production of slow muonic hydrogen isotopes in vacuum

Muonic hydrogen isotopes (μ⁻ p, μ⁻ d, and μ⁻t) are simple quantum mechanical systems ideally suited for studies of numerous fundamental phenomena in electroweak and strong interactions as well as in applied areas such as muon chemistry or muon catalyzed fusion. Emission of muonic hydrogen isotopes into vacuum helps to overcome the limitations which are normally imposed on conventional investigations with gaseous and liquid targets. A proof of principle experiment for this new technique was performed at TRIUMF last year. Negative muons with 30 MeV/c momentum were stopped in a thin film of solid hydrogen and produced very low energy μ⁻d in vacuum. The distribution center of the normal velocity components of emitted μ⁻d atoms was measured to be ∼1 cm/μs. The yield of μ⁻d in vacuum is an increasing function of H₂ film thickness δ up to a value of δ≥1 mm.     

Quantum diffusion of muonium in GaAs

The diffusion rate of muonium in the III–V compound semiconductor GaAs has been determined from measurements of muon spinT ₁ relaxation induced by motion in the presence of nuclear hyperfine interactions. It is shown for the first time in a semiconductor that (a) there is a crossover of the transport mechanism at about 90 K from stochastic to zero-phonon hopping, as evidenced by a steep rise in the hop rate at lower temperatures, and that (b) the muonium diffuses at the hop rate of 10¹⁰ s⁻¹ (corresponding diffusion constantD≈10⁻⁶ cm²s⁻¹) at lower temperatures as well as at room temperature.     

Mössbauer spectra and magnetic properties of Sm2 (Co,Fe)17 alloys

Hyperfine Interactions - Sm2(Co1?x Fe x )17 alloys form the basis of a new class of permanent magnets. We have investigated these materials with57Fe Mössbauer spectroscopy. Alloys...     

Fast switching ferroelectric side-chain liquid-crystalline polymer and copolymer

New ferroelectric side-chain liquid-crystalline polymers, a copolymer and a homopolymer, with siloxane backbone and a triaromatic mesogen as the side group have been synthesized. The materials exhibit a chiral smectic C phase over a large temperature range extending to room temperature. They possess high values of spontaneous polarization: 105 nC cm^-2 for the homopolymer and 180 nC cm^-2 for the copolymer. The electro-optic switching time in the chiral smectic C phase is extremely fast (150 μs). In the smectic A phase, an electroclinic effect with switching times less than 100 μs and with field induced tilt angles of 18° is observed.     

Superconvergence of recovered gradients of discrete time/piecewise linear Galerkin approximations for linear and nonlinear parabolic problems

Superconvergent error estimates in l₂(H¹) and l∞(H¹) norms are derived for recovered gradients of finite difference in time/piecewise linear Galerkin approximations in space for linear and quasinonlinear parabolic problems in two space dimensions. The analysis extends previous results for elliptic problems to the parabolic context, and covers problems in regions with nonsmooth boundaries under certain assumptions on the regularity of the solutions. © 1994 John Wiley & Sons, Inc.     

Rotational Spectra of Argon Acetone: A Two-Top Internally Rotating Complex

The rotational spectra of the argon acetone weakly bound complex was studied by pulsed jet Fabry-Perot Fourier transform microwave spectroscopy. Over 500 transitions of the complex were measured between 5.5 and 26 GHz from J=2-1 to J=12-11. The two methyl groups undergo hindered internal rotation resulting in four or five internal rotation states. The microwave transitions are within these states, resulting in a splitting of each rotational transition into four and sometimes five distinct transitions. The three-fold barrier to internal rotation is determined to be 260 cm⁻¹, 2% less than the 266 cm⁻¹ barrier in acetone itself. The structure of the complex has the argon atom above the heavy atom plane of the acetone, 3.52 Å from the CO bond and approximately in the C_s plane, which is perpendicular to the CCC plane of acetone.