Determination of domain sizes in blends of poly(ethylene) and poly(styrene) formed in the presence of supercritical carbon dioxide

Well-mixed blends of poly(ethylene) and poly(styrene) have been synthesized using supercritical carbon dioxide as a solvent. The morphology of the blends has been conclusively characterized using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), Raman microprobe microscopy, and C-13 solid-state cross-polarization magic angle spinning NMR (C-13 CPMAS NMR). DSC measurements demonstrate that poly(styrene) in the blends resides solely in the amorphous regions of the poly(ethylene) matrix; however, corroborative evidence from the SAXS experiments shows that poly(styrene) resides within the interlamellar spaces. The existence of nanometer-sized domains of poly(styrene) was shown within a blend of poly(styrene) and poly(ethylene) when formed in supercritical carbon dioxide using Raman microprobe microscopy and C-13 CPMAS NMR spectroscopy coupled with a spin diffusion model. This contrasts with blends formed at ambient pressure in the absence of solvent, in which domains of poly(styrene) in the micrometer size range are formed. This apparent improved miscibility of the two components was attributed to better penetration of the monomer prior to polymerization and increased swelling of the polymer substrate by the supercritical carbon dioxide solvent.

Quantum trajectories for the realistic measurement of a solid-state charge qubit

We present a new model for the continuous measurement of a coupled quantum dot charge qubit. We model the effects of a realistic measurement, namely adding noise to, and filtering, the current through the detector. This is achieved by embedding the detector in an equivalent circuit for measurement. Our aim is to describe the evolution of the qubit state conditioned on the macroscopic output of the external circuit. We achieve this by generalizing a recently developed quantum trajectory theory for realistic photodetectors [P. Warszawski, H. M. Wiseman, and H. Mabuchi, Phys. Rev. A 65, 023802 (2002)] to treat solid-state detectors. This yields stochastic equations whose (numerical) solutions are the realistic quantum trajectories of the conditioned qubit state. We derive our general theory in the context of a low transparency quantum point contact. Areas of application for our theory and its relation to previous work are discussed.

Global control and fast solid-state donor electron spin quantum computing

We propose a scheme for quantum information processing based on donor electron spins in semiconductors, with an architecture complementary to the original Kane proposal. We show that a naive implementation of electron spin qubits provides only modest improvement over the Kane scheme, however through the introduction of global gate control we are able to take full advantage of the fast electron evolution timescales. We estimate that the latent clock speed is 100-1000 times that of the nuclear spin quantum computer with the ratio T-2/T-ops approaching the 10(6) level.

The hydration of paper studied with solid-state magnetisation-exchange H-1 NMR spectroscopy

The wide-line H-1 nuclear magnetic resonance (NMR) spectrum of paper in equilibrium with ambient humidity consists of super-imposed relatively broad and narrow lines. The narrower line is of the order of 2 kHz wide at half the maximum height, while the broader line is of the order of 40 kHz in width at half height. On the basis of these line widths, the narrow line is assigned to water sorbed to the paper, and the broad line to the polymeric constituents of the paper. It was not possible to distinguish between the various polymeric components of paper contributing to the H-1 NMR spectra. A modified Goldman-Shen pulse sequence was used to generate a spatial magnetisation gradient between the polymer and water phases. The exchange of magnetisation between protons associated with water and those associated with the macromolecules in paper was observed. The exchange of magnetisation is discussed within a heat transfer model for homonuclear dipolar coupling, with exchange being characterised by a spin-diffusion coefficient. Consideration of the magnitude of the initial rate of the exchange process and estimates of the spin-spin relaxation times based on H-1 line widths indicate that some water must exist in a sufficiently immobile state as to allow homonuclear dipolar interactions between adjacent polymer and water protons. Thus, water sorbed onto paper must exist in at least two states in mass exchange with each other. This observation allows certain conclusions to be drawn about the ratio of free/bound water as a function of moisture content and the dispersal of water within the polymer matrix.

Numerical method for determination of the NMR frequency of the single-qubit operation in a silicon-based solid-state quantum computer

A numerical method is introduced to determine the nuclear magnetic resonance frequency of a donor (P-31) doped inside a silicon substrate under the influence of an applied electric field. This phosphorus donor has been suggested for operation as a qubit for the realization of a solid-state scalable quantum computer. The operation of the qubit is achieved by a combination of the rotation of the phosphorus nuclear spin through a globally applied magnetic field and the selection of the phosphorus nucleus through a locally applied electric field. To realize the selection function, it is required to know the relationship between the applied electric field and the change of the nuclear magnetic resonance frequency of phosphorus. In this study, based on the wave functions obtained by the effective-mass theory, we introduce an empirical correction factor to the wave functions at the donor nucleus. Using the corrected wave functions, we formulate a first-order perturbation theory for the perturbed system under the influence of an electric field. In order to calculate the potential distributions inside the silicon and the silicon dioxide layers due to the applied electric field, we use the multilayered Green's functions and solve an integral equation by the moment method. This enables us to consider more realistic, arbitrary shape, and three-dimensional qubit structures. With the calculation of the potential distributions, we have investigated the effects of the thicknesses of silicon and silicon dioxide layers, the relative position of the donor, and the applied electric field on the nuclear magnetic resonance frequency of the donor.

Oxoketene-oxoketene, imidoylketene-imidoylketene and oxoketenimine-imidoylketene rearrangements. 1,3-shifts of phenyl groups

Dibenzoylketene 5 undergoes degenerate 1,3-shifts of the phenyl group between acyl and ketene carbon atoms, thus interconverting it with 6 and 7. This 1,3-shift takes place in the gas phase under flash vacuum thermolysis (FVT) conditions, but not in solution at 110-145 degrees C. Imidoyl(benzoyl)ketene 13 undergoes degenerate 1,3-shift of the phenyl group on FVT, thus interconverting it with 14, but the ketenimine isomer 15 is not formed, and none of these shifts take place in the solid state at 250 degrees C. Imidoyl(p-toluoyl)ketene 21 undergoes a 1,3-p-tolyl shift, interconverting it with ketene 22 but not with ketenimine 23. The imidoyl(p-toluoyl)ketene rotamer 25 cyclizes to 4-toluoyloxyquinoline 28 and 4-quinolone 29. The cyclization of imidoyl(benzoyl)ketene 13 to 4-benzoyloxyquinoline 18, and of 25 to 28 involves 1,3-C-to-O shifts of benzoyl (toluoyl) groups. Calculations of the transition states for the transformations at the B3LYP/6-31G** level of theory are in agreement with the observed reaction preferences.