Sorption and diffusion of toluene in isotropic and oriented linear polyethylene

Sorption and diffusion of toluene vapor in linear polyethylene with mass-fraction crystallinity between 0.48 and 0.82 and draw ratios λ up to 10 have been studied at 30°C. The sorbed concentration in the amorphous phase C_a is little affected by crystallinity, indicating that the free-volume fraction is roughly the same for all isotropic samples. However, the diffusion path becomes more tortuous with increasing crystalline content, thereby leading to a sixfold drop in the zero-concentration diffusion coefficient D₀. Drawing has more drastic effects, reducing C_a and D₀ by factors of 4 and 60, respectively, as λ increases to 10. These large changes result from the transformation of the initially spherulitic material into a fibrous structure, which is composed of aligned microfibrils with taut tie molecules lying on the outer boundaries. The effects of crystallinity and orientation on the concentration dependence of the diffusion coefficient are also discussed.     

Copper(II) and nickel(II) complexes of a neutral pentadentate Schiff base

A new pentadentate Schiff base 2,6,10-triaza-1,11-bis(2′-aminophenyl)-undeca-1,10-diene, abaDPT, and its complexes of general formula M(abaDPT)X₂ where M = Cu(II), Ni(II), X = Cl, Br, I, NO₃ and ClO₄, have been prepared. The complexes have been characterized by electronic and IR spectra, EPR, magnetic moments, molar conductances, and elemental analysis. IR data show an interaction between halide anion of the outer coordination sphere and the complexed amino group. EPR and spectrophotometric data of most of the copper compounds are consistent with a distorted square pyramidal geometry. Single crystal EPR studies of Cu(abaDPT)(NO₃)₂ and Cu(abaDPT)Br₂ revealed that copper atoms in the former compound occupy two magnetically inequivalent places in the lattice while copper atoms in the latter compound take identical sites. Principal g tensor axes of the two compounds have been determined.     

A stereoselective cyclization to carbafuranose derivatives starting from 1,4-bis-epoxides

[reactions: see text] A concise synthesis of highly functionalized cyclopentane derivatives via a Brook rearrangement mediated stereoselective linchpin cyclization reaction involving tert-butyldimethylsilyl-1,3-dithianyllithium and homochiral 1,4-bis-epoxides is described.     

Probing the interior of neutron stars with gravitational waves

We show here how the internal structure of a neutron star can be inferred from its gravitational wave spectrum. Under the premise that the frequencies and damping rates of a few w-mode oscillations are found, we apply an inversion scheme to determine its mass, radius, and density distribution. In addition, an accurate equation of state of nuclear matter can also be determined.     

High-resolution angular measurement using surface-plasmon-resonance via phase interrogation at optimal incident wavelengths

It is demonstrated that ultrahigh-resolution angular measurement can be achieved via surface-plasmon-resonance excitation in which the phase difference between p- and s-polarized reflected waves is monitored as a function of the incidence angle. Resolutions down to 1.9 x 10(-6) deg are obtained by performing the measurements at optimal incident wavelengths. This represents an order of magnitude improvement compared with previously reported values.     

Nonexistence of abelian difference sets: Lander's conjecture for prime power orders

In 1963 Ryser conjectured that there are no circulant Hadamard matrices of order 4$"> and no cyclic difference sets whose order is not coprime to the group order. These conjectures are special cases of Lander's conjecture which asserts that there is no abelian group with a cyclic Sylow -subgroup containing a difference set of order divisible by . We verify Lander's conjecture for all difference sets whose order is a power of a prime greater than 3.

     

Low-threshold quantum-cascade lasers at 3.5 THz (lambda = 85 microm)

Chirped-superlattice quantum-cascade lasers are reported that emit at lambda approximately 85 microm (3.6 THz), which is to the authors' knowledge the longest wavelength demonstrated so far with this technology. Collected peak output powers of 1.5 mW per facet were measured at liquid-helium temperature, and a maximum operating temperature of 45 K was reached. Record low-threshold-current densities of 95 and 115 A cm(-2) were observed in pulsed and continuous-wave operation, respectively. For the latter, output powers of a few hundred microwatts are estimated at low temperatures.     

Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

Low-energy spectra in t-J-type models at low doping levels

Based on a variational approach, we propose that there are two kinds of low-energy states in the t-J-type models at low doping. In a quasiparticle state an unpaired spin bound to a hole with a well-defined momentum can be excited with spin waves. The resulting state shows a suppression of antiferromagnetic order around the hole with the profile of a spin bag. These spin-bag states with spin and charge or hole separated form a continuum of low-energy excitations. Very different properties predicted by these two kinds of states explain a number of anomalous results observed in the exact diagonalization studies on small clusters up to 32 sites.     

Precursor film controlled wetting of Pb on Cu

Wetting in a system where the kinetics of drop spreading are controlled by the rate of formation of a precursor film is modeled for the first time at the atomistic scale. Molecular dynamics simulations of Pb(l) wetting Cu(111) and Cu(100) show that a precursor film of atomic thickness evolves and spreads diffusively. This precursor film spreads significantly faster on Cu(111) than on Cu(100). For Cu(100), the kinetics of drop spreading are dramatically decreased by slow advancement of the precursor film. Slow precursor film kinetics on Cu(100) are partly due to the formation of a surface alloy at the solid-liquid interface which does not occur on Cu(111).