Image-potential surface states on Ag(100): A reinvestigation

Employing inverse photoemission we have remeasured the energy dispersionE(k) of the lowest-lying image state on Ag(100) with improved energy resolution (electrons and photons, E=0.35 eV) andk-resolution (k<0.1 Å^–1). In a least-square fit with the binding energyE _B atk=0 and the effective massm ^* as parameters we obtainE _B =E _vac –0.67 eV andm ^*=1.5 m in agreement with our earlier findings but differing from the two-photon photoemission values (0.53 eV and 1.15 m).     

Analysis of SM8 and Zap TK calculations and their geometric sensitivity

A prospective study of aqueous solvation energies was done using the SM8 and Zap TK models for a variety of geometries. CM4M charges calculated with M06 and M06-2X were found to yield similar results for the SM8 model. Zap TK calculations were primarily done with AM1BCC charges but limited attempts to use charges derived from DFT showed promise. The OMEGA application quickly generated conformations that performed well with both solvation models, while the use of computationally expensive DFT optimized geometries yielded increased RMSE and MSE. It is shown that increasing levels of gas phase geometry optimization yield increasingly unfavorable solvation energy for single conformer models.     

Mechanical properties of zinc and calcium phosphates

Recent studies on a variety of metal phosphates (MP) have revealed that MPs tend to be soft at ambient pressure if the coordination on the metal cation is low and the degree of hydration or hydrogenation is high, while they are stiff otherwise. In addition, the softer MPs were found to stiffen dramatically more quickly with increasing pressure than the stiffer MPs. Here we review these findings and support their relevance with new results on the mechanical properties of tribofilms aged in air of relative humidity, which were produced from commercial, zinc phosphate-containing lubricant packages via heating and rubbing. We find that the films can soften quite substantially after having been exposed to humidity, as to be expected from the studies of bulk MPs. Moreover, when the hydrated films are exposed to high loads, the force-distance withdrawal curve becomes identical to that of unaged, non-hydrated films. A straightforward explanation of this observation is that large pressure reverses the hydration of the tribofilms.     

Error analysis of an enhanced DtN-FE method for exterior scattering problems

In this work we analyze the convergence of the high-order Enhanced DtN-FEM algorithm, described in our previous work (Nicholls and Nigam, J. Comput. Phys. 194:278–303, 2004), for solving exterior acoustic scattering problems in . This algorithm consists of using an exact Dirichlet-to-Neumann (DtN) map on a hypersurface enclosing the scatterer, where the hypersurface is a perturbation of a circle, and, in practice, the perturbation can be very large. Our theoretical work had shown the DtN map was analytic as a function of this perturbation. In the present work, we carefully analyze the error introduced by virtue of using this algorithm. Specifically, we give a full account of the error introduced by truncating the DtN map at a finite order in the perturbation expansion, and study the well-posedness of the associated formulation. During computation, the Fourier series of the Dirichlet data on the artificial boundary must be truncated. To deal with the ensuing loss of uniqueness of solutions, we propose a modified DtN map, and prove well-posedness of the resulting problem. We quantify the spectral error introduced due to this truncation of the data. The key tools in the analysis include a new theorem on the analyticity of the DtN map in a suitable Sobolev space, and another on the perturbation of non-self-adjoint Fredholm operators.     

Lingos, finite state machines, and fast similarity searching

We apply a recently published method of text-based molecular similarity searching (LINGO) to standard data sets for the purpose of quantifying the accuracy of the approach. Our implementation is based on a pattern-matching finite state machine (FSM) which results in fast search times. The accuracy of LINGO is demonstrated to be comparable to that of a path-based fingerprint and offers a simple yet effective method for similarity searching.     

Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Stable computation of the functional variation of the Dirichlet–Neumann operator

This paper presents an accurate and stable numerical scheme for computation of the first variation of the Dirichlet–Neumann operator in the context of Euler’s equations for ideal free-surface fluid flows. The Transformed Field Expansion methodology we use is not only numerically stable, but also employs a spectrally accurate Fourier/Chebyshev collocation method which delivers high-fidelity solutions. This implementation follows directly from the authors’ previous theoretical work on analyticity properties of functional variations of Dirichlet–Neumann operators. These variations can be computed in a number of ways, but we establish, via a variety of computational experiments, the superior effectiveness of our new approach as compared with another popular Boundary Perturbation algorithm (the method of Operator Expansions).