Hydration of mineral surfaces probed at the molecular level

By employing the nonlinear optical, interface selective experiment of sum frequency spectroscopy together with independent ab initio and density functional theory calculations, we determine the functional species of a corundum (001) surface: doubly coordinated OH groups which differ in their bond tilt angles. The interaction of the functional species with the adjacent water molecules is also observed. In a large pH range around the point of zero charge, the interaction is not controlled electrostatically but by hydrogen bonding. The functional species' tilt angles are crucial parameters, determining whether the species act as hydrogen bond donors or acceptors.     

An Evaluation of Primer Preseating in Small Caliber Cartridge Production

This work presents the findings of a study to quantify the relative effectiveness of the primer preseating operation in small caliber cartridge production. In theory, primer preseating would enable cartridge stamping tools to achieve deeper stamping penetration depths and subsequently, greater primer retention forces. This is because, with preseating incorporated in the existing small caliber cartridge production process, a cartridge stamping tool would be fully dedicated to performing the case stamping operation (rather than the simultaneous primer seating and case stamping operations it currently performs). The findings presented in this work include measured percentages of total stamping tool force dedicated to primer seating, stamping tool penetration depths with and without primer preseating and primer retention forces with and without primer preseating. These findings and their underlying principles were produced through a static force equilibrium analysis and finite element modeling and simulation studies.     

Formaldehyde Formation on Vanadium Oxide Surfaces V2O3(0001) and V2O5(001): How does the Stable Methoxy Intermediate Form?

Hydroxy‐mediated methoxy formation or stabilization is probably an important process in many methanol adsorption systems. Hydrogen atoms originating from the scission of the methanol O? H bond react with the substrate and form water. This process may result 1) in the production of additional surface defects as reactive centers for methoxy formation and 2) in the stabilization of methoxy groups by suppression of methanol formation.

     

Towards a force field based on density fitting

Total intermolecular interaction energies are determined with a first version of the Gaussian electrostatic model (GEM-0), a force field based on a density fitting approach using s-type Gaussian functions. The total interaction energy is computed in the spirit of the sum of interacting fragment ab initio (SIBFA) force field by separately evaluating each one of its components: electrostatic (Coulomb), exchange repulsion, polarization, and charge transfer intermolecular interaction energies, in order to reproduce reference constrained space orbital variation (CSOV) energy decomposition calculations at the B3LYP/aug-cc-pVTZ level. The use of an auxiliary basis set restricted to spherical Gaussian functions facilitates the rotation of the fitted densities of rigid fragments and enables a fast and accurate density fitting evaluation of Coulomb and exchange-repulsion energy, the latter using the overlap model introduced by Wheatley and Price [Mol. Phys. 69, 50718 (1990)]. The SIBFA energy scheme for polarization and charge transfer has been implemented using the electric fields and electrostatic potentials generated by the fitted densities. GEM-0 has been tested on ten stationary points of the water dimer potential energy surface and on three water clusters (n = 16,20,64). The results show very good agreement with density functional theory calculations, reproducing the individual CSOV energy contributions for a given interaction as well as the B3LYP total interaction energies with errors below kBT at room temperature. Preliminary results for Coulomb and exchange-repulsion energies of metal cation complexes and coupled cluster singles doubles electron densities are discussed.     

Experimental test of special relativity by laser spectroscopy

The Doppler-free laser-spectroscopic frequency measurement of Doppler-shifted optical lines in forward and backward direction of a fast ion beam permits a sensitive test of the relativistic Doppler-formula and, hence, the relativistic time dilation factor . An experiment on metastable ⁷Li⁺, stored at a velocity of v = 0.064c in the Heidelberg heavy-ion storage ring TSR, has confirmed time dilation with unprecedented accuracy. Latest tests at two different ion-velocities (v = 0.03c and v = 0.064c) will enhance these measurements. An improved version of this experiment will be carried out at the experimental storage ring (ESR) at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt. The ESR permits ⁷Li⁺ to be stored at v = 0.33c which promises an improvement of the sensitivity to deviations from γ _SR by an order of magnitude. A first test at the ESR has shown the feasibility for this kind of experiment.     

The frequency of hard glottal attacks in patients with muscle tension dysphonia, unilateral benign masses and bilateral benign masses

Hard or abrupt glottal attack (HGA) is one of the vocal behaviors often associated with benign lesion of the vocal folds. This study was designed to determine whether the frequency of HGA was different in hyperfunctional voice patients with and without vocal fold masses. One hundred and forty-seven subjects were studied. All subjects received a complete otolaryngological evaluation including strobovideolaryngoscopy, objective voice measures, and evaluation by a speech-language pathologist. Thirty-two patients were diagnosed with muscle tension dysphonia (19 male, 13 female) without vocal fold masses. Fifty-seven patients were diagnosed with unilateral vocal fold masses (29 male, 28 female), most of which were cysts. Fifty-eight patients were diagnosed with bilateral vocal fold masses (13 male, 45 female). Of the 45 females with bilateral vocal fold masses. 26 had a vocal cyst and reactive nodule and 19 had bilateral vocal fold nodules. The control group was balanced and matched based on sex and on percentage of singers and nonsingers. It consisted of 49 subjects with no vocal fold pathology (20 male, 29 female). The group was composed of professional speakers, singers, and nonprofessional speakers. All voice disordered groups demonstrated higher frequencies of HGA than the control group. Differences were found between the male and female subjects in this study. No differences were found between the various disorders. Differences were also found between the subgroups of bilateral masses, where the bilateral nodules group presented a higher frequency of HGA than the cyst and contralateral reactive nodule.     

Computer Assisted Proof of Transverse Saddle-to-Saddle Connecting Orbits for First Order Vector Fields

In this paper we introduce a computational method for proving the existence of generic saddle-to-saddle connections between equilibria of first order vector fields. The first step consists of rigorously computing high order parametrizations of the local stable and unstable manifolds. If the local manifolds intersect, the Newton–Kantorovich theorem is applied to validate the existence of a so-called short connecting orbit. If the local manifolds do not intersect, a boundary value problem with boundary values in the local manifolds is rigorously solved by a contraction mapping argument on a ball centered at the numerical solution, yielding the existence of a so-called long connecting orbit. In both cases our argument yields transversality of the corresponding intersection of the manifolds. The method is applied to the Lorenz equations, where a study of a pitchfork bifurcation with saddle-to-saddle stability is done and where several proofs of existence of short and long connections are obtained.     

The effective potential of the confinement order parameter in the Hamiltonian approach

The effective potential of the order parameter for confinement is calculated within the Hamiltonian approach by compactifying one spatial dimension and using a background gauge fixing. Neglecting the ghost and using the perturbative gluon energy one recovers the Weiss potential. From the full non-perturbative potential calculated within a variational approach a critical temperature of the deconfinement phase transition of 269 MeV is found for the gauge group SU(2).