Quasiclassical trajectory calculations to evaluate a kinematic constraint on internal energy in suprathreshold collision energy abstraction reactions

Experimentally observed product quantum state distributions across a wide range of abstraction reactions at suprathreshold collision energies have shown a strong bias against product internal energy. Only a fraction, sometimes quite a small fraction, of the energetically accessible product quantum states are populated. Picconatto et al. [J. Chem. Phys. 114, 1663 (2001)] noted a simple mathematical relationship between the highest-energy rovibrational states observed and the kinematics of the reaction system. They proposed a reaction model based on reaction kinematics that quantitatively explains this behavior. The model is in excellent agreement with measured quantum state distributions. The assumptions of the model invoke detailed characteristics of reactive trajectories at suprathreshold collision energies. Here we test those assumptions using quasiclassical trajectory calculations for the abstraction reactions H+HCl-->H2+Cl, D+HCl-->HD+Cl, and H+DCl-->HD+Cl. Trajectories were run on a potential-energy surface calculated with a London-Eyring-Polyani-Sato function with a localized 3-center term (LEPS-3C) previously shown to accurately reproduce experimentally observed product state distributions for the H+HCl abstraction reaction. The trajectories sample collision energies near threshold and also substantially above it. Although the trajectories demonstrate some aspects of the model, they show that it is not valid. However, the inadequacy of the proposed model does not invalidate the apparent kinematic basis of the observed energy constraint. The present results show that there must be some other molecular behavior rooted in the reaction kinematics that is the explanation and the source of the constraint.     

An explanation of the unusual strength of the hydrogen bond in small water clusters

We seek to explain why the hydrogen bond possesses unusual strength in small water clusters that account for many of the complex behaviors of water. We have investigated and visualized the donation of covalent character from covalent (sigma) to hydrogen bonds by calculating the eigenvector coupling properties of quantum theory of atoms in molecules (QTAIM), stress tensor σ ( r ), and Ehrenfest Force F ( r ) on the F ( r ) molecular graph. The next-generation three-dimensional (3-D) bond-path framework sets are presented, and only the F ( r ) bond-path framework sets reproduce the earlier finding on the coupling between covalent (sigma) and hydrogen bonds that possess a degree of covalent character. Exploration of the bond-path between the covalent (sigma) and hydrogen bond's critical points provides an explanation for the previously obtained coupling results. The directional character of the covalent (sigma) and hydrogen bonds' 3-D bond-path framework sets for the F ( r ) explains differences found in the earlier results from QTAIM and the stress tensor σ ( r ).     

Electron attachment to propargyl chloride, 305-540 K

Electron attachment to propargyl chloride (HC≡C-CH(2)Cl) was studied in a flowing-afterglow Langmuir-probe apparatus from 305 to 540 K. The sole ion product in this temperature range is Cl(-). Electron attachment is very inefficient, requiring correction for a competing process of electron recombination with molecular cations produced in reaction between Ar(+) and propargyl chloride and subsequent ion-molecule reactions. The electron attachment rate coefficient was measured to be 1.6×10(-10)cm(3)?s(-1) at 305 K and increased to 1.1×10(-9)cm(3)?s(-1) at 540 K.     

Electron-catalyzed mutual neutralization of various anions with Ar+: evidence of a new plasma process

The mutual neutralization of anions with Ar+ has been studied by variable electron and neutral density attachment mass spectrometry. Evidence of a previously unobserved plasma loss process, electron-catalyzed mutual neutralization (ECMN), e.g., SF6-+Ar+ + e-→neutrals + e-, is reported. Results for 10 species suggest that ECMN occurs generally and significantly affects the total ion-loss rate in plasmas with electron densities exceeding 10(10) cm-3. ECMN is discussed in the context of other known three-body plasma processes, the mechanisms for which appear insufficient to explain the observed effect. A mechanism for ECMN involving an incident electron facilitating energy transfer to the internal modes of the anion is proposed.     

Small-angle x-ray scattering in a carbon-sulfur nanocomposite produced from bulk nanoporous carbon

A new nanocomposite material containing approximately 50 vol % S is prepared by filling pores of bulk nanoporous carbon samples with sulfur. The initial nanoporous carbon samples are synthesized from polycrystalline α-SiC through the chemical reaction. A comparative investigation of small-angle x-ray scattering (SAXS) is performed for the prepared nanocomposite and the initial material. The possible changes in the scattering power of the initial material upon filling of its pores with sulfur are considered in the framework of a simple model. The regularities revealed are used to interpret the experimentally observed changes in the scattering power. The size distribution functions of incorporated sulfur nanoclusters in the nanocomposite (or filled nanopores in the initial material) are determined within the Guinier approximation. It is demonstrated that the smallest sized pores (8–16 Å) remain unfilled, whereas the filling factor for larger sized pores can reach several ten percent by volume. The conditions favorable for small-angle x-ray scattering upon filling of the nanopores are analyzed.     

Shielding against noise interfering with quantitation of insect infestations by acoustic detection systems in grain elevators

Acoustic devices used to detect hidden insect infestations must be shielded from noise in most practical applications. One device developed specifically for use in a noisy environment, the Acoustic Location ‘Fingerprinting’ Insect Detector (ALFID), counts the numbers of insects present in grain samples from shipments being graded for export at commercial grain elevators. This report considers the performance of ALFID's noise-shielding components, which include an enclosure for passive reduction of ambient noise, and an electronic system for active detection and masking of sounds originating outside the grain sample container. Sound pressure levels (SPLs) of ambient noise are reduced inside the enclosure by 60–90 dB at frequencies between 1 and 10 kHz, with a reduction of ~6.5 dB per octave (frequency doubling). The active noise-masking system protects ALFID from loud ambient sounds not sufficiently attenuated by the enclosure. If the output from one of four sensors mounted on the outside of the grain sample container rises above a preset amplitude threshold, a signal is triggered that inhibits acquisition of insect sound data from sensors inside the container. In tests of the complete ALFID system at a grain elevator with ambient noise of 73 ± W dB re 20 μPa SPL, the mean rate of noise-mask triggering was 5.5 s⁻¹, inhibiting acquisition of insect sounds for only 3.9% of the total testing period. This level of performance is sufficient to enable successful operation of ALFID under such noise conditions.     

Complete signal processing bases and the Jacobi group

The continuous windowed Fourier and wavelet transforms are created from the actions of the Heisenberg and affine groups, respectively. Both wavelet and windowed Fourier bases are known to be complete; that is, the only signal which is orthogonal to every element of each basis is the zero signal. The Jacobi group is a group which contains both the Heisenberg and affine groups, and it can also be used to produce bases for signal processing. This paper investigates completeness for bases of one and two real variables which are produced by the Jacobi group.     

Image holography through convective fog

Light experiences a Doppler frequency shift if it is deflected by scattering on a moving particle. In holography that situation occurs when the light on the way from the object to the hologram passes through moving fog. Due to the Doppler shift the scattered light cannot interfere with the undisturbed reference wave. Hence only the unscattered portion of the object wave contributes to the interference fringes on the hologram. Therefore the reconstructed image is not blurred due to scattering in the fog. We present a simple theory of holographic vision through fog and some verifying experiments.