Application of static charge transfer within an ionic-liquid force field and its effect on structure and dynamics

The effects of linear scaling of the atomic charges of a reference potential on the structure, dynamics, and energetics of the ionic liquid 1,3-dimethylimidazolium chloride are investigated. Diffusion coefficients that span over four orders of magnitude are observed between the original model and a scaled model in which the ionic charges are +/- 0.5 e. While the three-dimensional structure of the liquid is less affected, the partial radial distribution functions change markedly-with the positive result that for ionic charges of +/- 0.7 e, an excellent agreement is observed with ab initio molecular dynamics data. Cohesive energy densities calculated from these partial-charge models are also in better agreement with those calculated from the ab initio data. We postulate that ionic-liquid models in which the ionic charges are assumed to be +/- 1 e overestimate the intermolecular attractions between ions, which results in overstructuring, slow dynamics, and increased cohesive energy densities. The use of scaled-charge sets may be of benefit in the simulation of these systems-especially when looking at properties beyond liquid structure-thus providing on alternative to computationally expensive polarisable force fields.

Positronium scattering by atomic hydrogen with inclusion of target excitation channels

Calculations are reported for positronium (Ps) scattering by atomic hydrogen (H) in the energy range 0-6.5 eV in a coupled- pseudostate approximation in which excitation and ionization channels of both the Ps and the H are taken into account. The approximation contains an accurate representation of the van der Waals coefficient. Results are presented for phase shifts, scattering lengths, effective ranges, and various cross sections including partial wave, total, and ortho-para conversion cross sections. An analysis of the possible spin transitions is provided and the energy of the positronium hydride (PsH) bound state is determined. Substantial differences are found from earlier work within the frozen target approximation, now clearly confirming the importance of target excitation channels. Good agreement is obtained with recent calculations of S-wave phase shifts and scattering lengths using the stabilization method. Convergence to the exact binding energy for PsH appears to be slow. Resonances corresponding to unstable states of the positron orbiting H- are seen in the electronic spin singlet partial waves. The importance of the H- formation channel is discussed.

Total cross sections for transfer ionization in fast ion-helium collisions

The effects of electron correlation and second-order terms on theoretical total cross sections of transfer ionization in collisions of the helium atom with fast H+, He2+ and Li3+ ions are studied and reported. The total cross sections are calculated using highly correlated wavefunctions with expansion of the transition amplitude in the Born series through the second order. The results of these calculations are in sensible agreement with experimental data.

Total and single differential cross sections for simple resonant collisions using a fully orthonormal continuum-distorted-wave basis

Simple electron capture processes are studied using an orthonormal two state continuum-distorted-wave (CDW) basis. The suitability of the basis set is tested by comparing predictions for total and differential cross sections with available experimental data. Overall good agreement is obtained and the authors conclude that a relatively small CDW basis set may be suitable to model a wide variety of low-energy collisions if the members of this extended set are astutely chosen.

Electron-impact ionization of atomic hydrogen close to threshold

A systematic study of the ionization of atomic hydrogen by electron impact from 0.3 eV to a few eV above the ionization threshold has been carried out using a semiclassical-quantal calculation. Differential and integrated cross sections are presented at 0.3 eV above the energy threshold. Triple- differential cross sections (TDCS) are presented at constant theta(12) geometry where theta(12)=180degrees and 150degrees. Good agreement is achieved with the measurement [Roder, Phys. Rev. Lett. 79, 1666 (1997)] and calculations based on exterior complex scaling at 2 eV and 4 eV above threshold. Results of triple-differential cross sections are also presented at 0.3, 0.5, and 1.0 eV above threshold at both theta(12)=180degrees and 150degrees. At theta(12)=180degrees the small local maximum in the TDCS around theta(1)=90degrees reported by Pan and Starace [Phys. Rev. A 45, 4588 (1992)] at 0.5 eV above threshold is not observed in our calculation at energies down to 0.3 eV above threshold. The shape of our double differential cross sections seems to disagree qualitatively with the available calculations as we found two local maxima around 15degrees and 165degrees in our calculation. Single differential cross sections in our formulation appear naturally as a function of total excess energy E and, therefore, constant for all combinations of individual electron energies E-1 and E- 2 with E=E-1+E-2. Total ionization cross sections are also compared with measurement and available theoretical calculations and found to be in reasonably good agreement up to 10 eV above ionization threshold.

Magnetically quantized continuum distorted-wave theory in atomic and molecular collisions

The continuum distorted-wave eikonal initial-state (CDW-EIS) theory of Crothers and McCann (J Phys B 1983, 16, 3229) used to describe ionization in ion-atom collisions is generalized (G) to GCDW-EIS to incorporate the azimuthal angle dependence of each CDW in the final-state wave function. This is accomplished by the analytic continuation of hydrogenic-like wave functions from below to above threshold, using parabolic coordinates and quantum numbers including magnetic quantum numbers, thus providing a more complete set of states. At impact energies lower than 25 keVu(-1), the total ionization cross-section falls off, with decreasing energy, too quickly in comparison with experimental data. The idea behind and motivation for the GCDW-EIS model is to improve the theory with respect to experiment by including contributions from nonzero magnetic quantum numbers. We also therefore incidentally provide a new derivation of the theory of continuum distorted waves for zero magnetic quantum numbers while simultaneously generalizing it. (C) 2004 Wiley Periodicals, Inc.

Semiclassical treatment of Wannier's theory when the exponent diverges

We consider a non-standard application of the Wannier model. A physical example is the single ionization of a hydrogenic beryllium ion with a fully stripped beryllium ion, where the ratio of the charge of the third particle to the charges of the escaping particles is 1/4; we investigate the single ionization by an electron of an atom comprising an electron and a nucleus of charge 1/4. An infinite exponent is obtained suggesting that this process is not tractable within the Wannier model. A modified version of Crothers' uniform semiclassical wavefunction for the outgoing particles has been adopted, since the Wannier exponents and are infinite for an effective charge of Z = 1/4. We use Bessel functions to describe the Peterkop functions u and u and derive a new turning point ?. Since u is well behaved at infinity, there exists only the singularity in u at infinity, thus we employ a one- (rather than two-) dimensional change of dependent variable, ensuring that a uniform solution is obtained that avoids semiclassical breakdown on the Wannier ridge. The regularized final-state asymptotic wavefunction is employed, along with a continuum-distorted-wave approximation for the initial-state wavefunction to obtain total cross sections on an absolute scale. © 2006 IOP Publishing Ltd.

A simple model of atomic interactions in noble metals based explicitly on electronic structure

A total energy tight-binding model with a basis of just one s state per atom is introduced. It is argued that this simplest of all tight-binding models provides a surprisingly good description of the structural stability and elastic constants of noble metals. By assuming inverse power scaling laws for the hopping integrals and the repulsive pair potential, it is shown that the density matrix in a perfect primitive crystal is independent of volume, and structural energy differences and equations of state are then derived analytically. The model is most likely to be of use when one wishes to consider explicitly and self-consistently the electronic and atomic structures of a generic metallic system, with the minium of computation expense. The relationship to the free-electron jellium model is described. The applicability of the model to other metals is also considered briefly.

Partial and total multiphoton detachment rates for H- in a perturbative B-spline-based approach

An ab initio approach has been applied to study multiphoton detachment rates for the negative hydrogen ion in the lowest nonvanishing order of perturbation theory. The approach is based on the use of B splines allowing an accurate treatment of the electronic repulsion. Total detachment rates have been determined for two- to six-photon processes as well as partial rates for detachment into the different final symmetries. It is shown that B-spline expansions can yield accurate continuum and bound-state wave functions in a very simple manner. The calculated total rates for two- and three-photon detachment are in good agreement with other perturbative calculations. For more than three-photon detachment little information has been available before now. While the total cross sections show little structure, a fair amount of structure is predicted in the partial cross sections. In the two-photon process, it is shown that the detached electrons mainly have s character. For four- and six-photon processes, the contribution from the d channel is the most important. For three- and five-photon processes p electrons dominate the electron emission spectrum. Detachment rates for s and p electrons show minima as a function of photon energy. © 1994 The American Physical Society.

A '3-body' abrasion wear study of bioceramics for total hip joint replacements

The current study focuses on the effect of the material type and the lubricant on the abrasive wear behaviour of two important commercially available ceramic on ceramic prosthetic systems, namely, Biolox(R) forte and Bioloxl(R) delta (CeramTec AG, Germany). A standard microabrasion wear apparatus was used to produce '3-body' abrasive wear scars with three different lubricants: ultrapure water, 25 vol% new-born calf serum solution and 1 wt% carboxymethyl cellulose sodium salt (CMC-Na) solution. 1 mu m alumina particles were used as the abrasive. The morphology of the wear scar was examined in detail using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Subsurface damage accumulation was investigated by Focused Ion Beam (FIB) cross-sectional milling and Transmission Electron Microscopy (TEM). The effect of the lubricant on the '3-body' abrasive wear mechanisms is discussed and the effect of material properties compared. (C) 2009 Elsevier B.V. All rights reserved.

A density functional theory study of CO and atomic oxygen chemisorption on Pt(111)

Ab initio total energy calculations within a density functional theory framework have been performed for CO and atomic oxygen chemisorbed on the Pt(111) surface. Optimised geometries and chemisorption energies for CO and O on four high-symmetry sites, namely the top, bridge, fee hollow and hcp hollow sites, are presented, the coverage in all cases being 0.25 ML. The differences in CO adsorption energies between these sites are found to be small, suggesting that the potential energy surface for CO diffusion across Pt(111) is relatively flat. The 5 sigma and 2 pi molecular orbitals of CO are found to contribute to bonding with the metal. Some mixing of the 4 sigma and 1 pi molecular orbitals with metal states is also observed. For atomic oxygen, the most stable adsorption site is found to be the fee hollow site, followed in decreasing order of stability by the hcp hollow and bridge sites, with the top site being the least stable. The differences in chemisorption energies between sites for oxygen are larger than in the case of CO, suggesting a higher barrier to diffusion for atomic oxygen. The co-adsorption of CO and O has also been investigated. Calculated chemisorption energies for CO on an O/fcc-precovered surface show that of the available chemisorption sites, the top site at the oxygen atom's next-nearest neighbour surface metal atom is the most stable, with the other four sites calculated bring at least 0.29 eV less stable. The trend of CO site stability in the coadsorption system is explained in terms of a 'bonding competition' model. (C) 2000 Elsevier Science B.V. All rights reserved.

Coherent and stochastic contributions of compound resonances in atomic processes: Electron recombination, photoionization, and scattering

In open-shell atoms and ions, processes such as photoionization, combination (Raman) scattering, electron scattering, and recombination are often mediated by many-electron compound resonances. We show that their interference (neglected in the independent-resonance approximation) leads to a coherent contribution, which determines the energy-averaged total cross sections of electron- and photon-induced reactions obtained using the optical theorem. In contrast, the partial cross sections (e.g., electron recombination or photon Raman scattering) are dominated by the stochastic contributions. Thus, the optical theorem provides a link between the stochastic and coherent contributions of the compound resonances. Similar conclusions are valid for reactions via compound states in molecules and nuclei.

Approach to chaos in ultracold atomic and molecular physics: Statistics of near-threshold bound states for Li+CaH and Li+CaF

We calculate near-threshold bound states and Feshbach resonance positions for atom–rigid-rotor models of the highly anisotropic systems Li+CaH and Li+CaF. We perform statistical analysis on the resonance positions to compare with the predictions of random matrix theory. For Li+CaH with total angular momentum J=0 we find fully chaotic behavior in both the nearest-neighbor spacing distribution and the level number variance. However, for J>0 we find different behavior due to the presence of a nearly conserved quantum number. Li+CaF (J=0) also shows apparently reduced levels of chaotic behavior despite its stronger effective coupling. This may indicate the development of another good quantum number relating to a bending motion of the complex. However, continuously varying the rotational constant over a wide range shows unexpected structure in the degree of chaotic behavior, including a dramatic reduction around the rotational constant of CaF. This demonstrates the complexity of the relationship between coupling and chaotic behavior.