Some aspects of single-grain luminescence dating

Single-grain methods of luminescence dating have been developed in order to circumvent problems of variability among aliquots of the sample being dated. Sufficient single grains must be separated in order to make an appropriate interpretation of the variability among such grains. We describe an automated apparatus for sorting grains for routine age determinations by green light stimulation. The sorted grains are then available for study of their collective luminescence physics characteristics. Examples are given of statistical frequency functions of grain brightness obtained with the apparatus and their interpretation. These frequency functions are lognormal or similar, covering up to four orders of magnitude, with consequent implications for luminescence dating application.     

Time-Resolved Dynamics of Struvite Crystallization: Insights from the Macroscopic to Molecular Scale

The crystallization of magnesium ammonium phosphate hexahydrate (struvite) often occurs under conditions of fluid flow, yet the dynamics of struvite growth under these relevant environments has not been previously reported. In this study, we use a microfluidic device to evaluate the anisotropic growth of struvite crystals at variable flow rates and solution supersaturation. We show that bulk crystallization under quiescent conditions yields irreproducible data owing to the propensity of struvite to adopt defects in its crystal lattice, as well as fluctuations in pH that markedly impact crystal growth rates. Studies in microfluidic channels allow for time-resolved analysis of seeded growth along all three principle crystallographic directions and under highly controlled environments. After having first identified flow rates that differentiate diffusion and reaction limited growth regimes, we operated solely in the latter regime to extract the kinetic rates of struvite growth along the [100], [010], and [001] directions. In situ atomic force microscopy was used to obtain molecular level details of surface growth mechanisms. Our findings reveal a classical pathway of crystallization by monomer addition with the expected transition from growth by screw dislocations at low supersaturation to that of two-dimensional layer generation and spreading at high supersaturation. Collectively, these studies present a platform for assessing struvite crystallization under flow conditions and demonstrate how this approach is superior to measurements under quiescent conditions.     

Sub-Doppler infrared spectroscopy of CH2D radical in a slit supersonic jet: isotopic symmetry breaking in the CH stretching manifold

First high-resolution infrared absorption spectra in the fundamental symmetric/asymmetric CH stretching region of isotopically substituted methyl radical, CH(2)D, are reported and analyzed. These studies become feasible in the difference frequency spectrometer due to (i) high density radical generation via dissociative electron attachment to CH(2)DI in a discharge, (ii) low rotational temperatures (23 K) from supersonic cooling in a slit expansion, (iii) long absorption path length (64 cm) along the slit axes, and (iv) near shot noise limited absorption sensitivity (5 × 10(-7)/√(Hz)). The spectra are fully rovibrationally resolved and fit to an asymmetric top rotational Hamiltonian to yield rotational/centrifugal constants and vibrational band origins. In addition, the slit expansion collisionally quenches the transverse velocity distribution along the laser probe direction, yielding sub-Doppler resolution of spin-rotation structure and even partial resolution of nuclear hyperfine structure for each rovibrational line. Global least-squares fits to the line shapes provide additional information on spin-rotation and nuclear hyperfine constants, which complement and clarify previous FTIR studies [K. Kawaguchi, Can. J. Phys. 79, 449 (2001)] of CH(2)D in the out-of-plane bending region. Finally, analysis of the spectral data from the full isotopomeric CH(m)D(3-m) series based on harmonically coupled Morse oscillators establishes a predictive framework for describing the manifold of planar stretching vibrations in this fundamental combustion radical.     

Unitary cocycle representations of the Galilean line group: Quantum mechanical principle of equivalence

We present a formalism of Galilean quantum mechanics in non-inertial reference frames and discuss its implications for the equivalence principle. This extension of quantum mechanics rests on the Galilean line group, the semidirect product of the real line and the group of analytic functions from the real line to the Euclidean group in three dimensions. This group provides transformations between all inertial and non-inertial reference frames and contains the Galilei group as a subgroup. We construct a certain class of unitary representations of the Galilean line group and show that these representations determine the structure of quantum mechanics in non-inertial reference frames. Our representations of the Galilean line group contain the usual unitary projective representations of the Galilei group, but have a more intricate cocycle structure. The transformation formula for the Hamiltonian under the Galilean line group shows that in a non-inertial reference frame it acquires a fictitious potential energy term that is proportional to the inertial mass, suggesting the equivalence of inertial mass and gravitational mass in quantum mechanics.     

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.     

Decomposition of the photoabsorption continuum underlying the Schumann-Runge bands of 16O2—II. Role of the 1 3Πg state and collision-induced absorption

Measurements are presented of molecular oxygen photoabsorption cross-sections and pressure coefficients taken at selected minima between rotational lines of the Schumann-Runge band system. Both room-temperature and liquid-nitrogen-temperature results are presented from 1760–1980 Å, and corrections are applied for the effect of the wings of the rotational lines. Absorption into the B³∑^?_u and A³∑⁺_u⁺ and is found to be insufficient to account for the total observed cross-section, and it is proposed that transitions to the 1³Π_g valence state account for the remainder. The pressure dependence of the cross-sections is consistent with collision-induced enhancement of the intensities of the forbidden transitions X³∑^?_g → A³∑⁺_g and $\text{X}{}^3\text{∑}{}^{\mathrm{?}}{}_{\mathrm{g}}\text{→ 1}{}^3\text{Π}{}_{\mathrm{g}}$, while the temperature dependence of the pressure coefficients is not consistent with absorption due to stable (O₂)₂ dimers.