Ultra-Precise Mass Measurements Using the UW-PTMS

Based on the use of a single ion, isolated at the center of a cryogenically cooled Penning trap, an environment is produced which makes this mass spectrometer remarkably free of systematic errors. The most notable developments in our quest for an ultra-high accuracy instrument were (a) the compensation of the trapping potential, (b) the discovery that motional sidebands could manipulate radial energies, (c) the use of multiply-charged ions that could improve signal-to-noise, and (d) the use of an ultra-stable superconducting magnet/cryostat system with drift <0.010 ppb/h. The dominant systematic errors are associated with radial electric fields caused by image charges in the trap electrodes and with the rf-electrical drive field used to determine the harmonic axial resonance. To illustrate the potential of this improved spectrometer, the four-fold improved measurement of the proton's mass and the eight-fold improved measurement of oxygen's atomic mass will be described. This revised version was published online in July 2006 with corrections to the Cover Date.     

Representation of Isotropic Turbulence by Scalar Functions

The maximum number N(n) of scalar functions of wavevector needed to represent the general cumulant of order n of isotropic turbulence is determined. In addition to reproducing the known results that N(2) = 1, N(3) = 2, it is shown that N(4) = 4, N(5) = 4, N(6) = 9, etc.     

Stability of solutions bifurcating from multiple eigenvalues

Let X and Y be real Banach spaces and G:X × $\text{R}$ be a twice continuously differentiate function which is not necessarily linear. Suppose G(u₀, α₀) = 0 and the dimension of the null space of G_u(u₀, α₀) is m, where 1 ? m < ∞. Usually, S = {(u, α):G(u, α) = 0}, in a neighborhood of (u₀, α₀), consists of a finite number of curves emanating from (u₀, α₀). We will determine the stability of points, (u, α), in S (i.e., the maximum of the real parts of the spectrum of G_u(u, α) for each (u, α) ∈ S) using a general perturbation theorem of Kato. Our results contain as a special case the stability theorems of Crandall and Rabinowitz for the case m = 1. We will also tie our stability theorems together with some bifurcation results of Decker and Keller. Finally we apply our results to systems of reaction diffusion equations.     

Improving accuracy by subpixel smoothing in the finite-difference time domain

Finite-difference time-domain (FDTD) methods suffer from reduced accuracy when modeling discontinuous dielectric materials, due to the inhererent discretization (pixelization). We show that accuracy can be significantly improved by using a subpixel smoothing of the dielectric function, but only if the smoothing scheme is properly designed. We develop such a scheme based on a simple criterion taken from perturbation theory and compare it with other published FDTD smoothing methods. In addition to consistently achieving the smallest errors, our scheme is the only one that attains quadratic convergence with resolution for arbitrarily sloped interfaces. Finally, we discuss additional difficulties that arise for sharp dielectric corners.     

Symmetry reduction for molecular dynamics simulation of an imploding gas bubble

We propose a symmetry reduction technique whereby molecular dynamics (MD) simulations for spherically symmetric gas bubbles can be accelerated. Results for an imploding Xenon bubble containing 50 million particles—the smallest measured sonoluminescing system—are presented.     

Extreme statistics of complex random and quantum chaotic states

Complex random states have the statistical properties of the Gaussian and circular unitary ensemble eigenstates of random matrix theory. Even though their components are correlated by the normalization constraint, it is nevertheless possible to derive compact analytic formulas for their extreme values' statistical properties for all dimensionalities. The maximum intensity result slowly approaches the Gumbel distribution even though the variables are bounded, whereas the minimum intensity result rapidly approaches the Weibull distribution. Since random matrix theory is conjectured to be applicable to chaotic quantum systems, we calculate the extreme eigenfunction statistics for the standard map with parameters at which its classical map is fully chaotic. The statistical behaviors are consistent with the finite-N formulas.     

Magnetic edge-state excitons in zigzag graphene nanoribbons

We present first-principles calculations of the optical properties of zigzag-edged graphene nanoribbons (ZGNRs) employing the GW-Bethe-Salpeter equation approach with the spin interaction included. Optical response of the ZGNRs is found to be dominated by magnetic edge-state-derived excitons with large binding energy. The absorption spectrum is composed of a characteristic series of exciton states, providing a possible signature for identifying the ZGNRs. The edge-state excitons are charge-transfer excitations with the excited electron and hole located on opposite edges; they moreover induce a spin transfer across the ribbon, resulting in a photoreduction of the magnetic ordering. These novel characteristics are potentially useful in the applications.     

Monaural level discrimination under dichotic conditions

The ability to make judgments about the stimulus at one ear when a stimulus is simultaneously presented to the other ear was tested. Specifically, subjects discriminated the level of a 600 Hz target tone presented at the left ear while an identical-frequency distractor was simultaneously presented at the other ear. When there was no distractor, threshold was 0.7 dB. Threshold increased to 1.1 dB when a distractor with a fixed phase and level was introduced contra-aurally to the target. Further increases in threshold were observed when an across-presentation variability was introduced into the distractor phase (threshold of 1.6 dB) or level (threshold of 5.8 dB). When both the distractor level and phase varied, the largest threshold of 7.3 dB was obtained. These increases in threshold cannot be predicted by common binaural models, which assume that a target stimulus at one ear can be processed without interference from the stimulus at the nontarget ear. The measured thresholds are consistent with a model that utilizes two binaural dimensions that roughly correspond to the loudness and the position of a fused binaural image. The results show that, with binaurally fused tonal stimuli, subjects are unable to listen to one ear.     

Towards the Design of Optically Active Thiophene S-Oxides using Quantum Chemistry

The importance of axially chiral biaryls has risen steeply in the recent decades. This structural motif proved to be successful in catalytic asymmetric synthesis and the configuration of the biaryl axis is decisive for the biological activity. A new approach for the atroposelective synthesis of biaryls would be through a cycloaddition between an enantiopure phenyl-substituted thiophene S-oxide and an alkyne. Importantly, the chiral center of the thiophene S-oxide needs to be stable enough to avoid pyramidal inversion during the cycloaddition. Considering that the racemization of thiophene monoxides has been scarcely investigated so far, we perform a thorough quantum chemical study on the inversion barriers of a large number of chiral thiophene S-oxide derivatives. Our main goal is to identify substitution patterns leading to stable atropisomers at room temperature. Appealingly, the role of stereoelectronic effects and the position of the substituents as well as the importance of aromaticity on the pyramidal inversion barrier are elucidated for the first time.     

Synthesis of High χ–Low N Diblock Copolymers by Polymerization-Induced Self-Assembly

Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called “high χ–low N” diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains.