Electron-hole pairs during the adsorption dynamics of O2 on Pd(100) - Exciting or not?

During the exothermic adsorption of molecules at solid surfaces dissipation of the released energy occurs via the excitation of electronic and phononic degrees of freedom. For metallic substrates the role of the nonadiabatic electronic excitation channel has been controversially discussed, as the absence of a band gap could favour an easy coupling to a manifold of electronhole pairs of arbitrarily low energies. We analyse this situation for the highly exothermic showcase system of molecular oxygen dissociating at Pd(100), using time-dependent perturbation theory applied to first-principles electronic-structure calculations. For a range of different trajectories of impinging O2 molecules we compute largely varying electron-hole pair spectra, which underlines the necessity to consider the high-dimensionality of the surface dynamical process when assessing the total energy loss into this dissipation channel. Despite the high Pd density of states at the Fermi level, the concomitant non-adiabatic energy losses nevertheless never exceed about 5% of the available chemisorption energy. While this supports an electronically adiabatic description of the predominant heat dissipation into the phononic system, we critically discuss the non-adiabatic excitations in the context of the O2 spin transition during the dissociation process.Comment: 20 pages including 7 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.html [added two references, changed V_{fsa} to V_{6D}, modified a few formulations in interpretation of spin asymmetry of eh-spectra, added missing equals sign in Eg.(2.10)

Implementing antiretroviral therapy in rural communities: the Lusikisiki model of decentralized HIV/AIDS care.

Health worker shortages are a major bottleneck to scaling up antiretroviral therapy (ART), particularly in rural areas. In Lusikisiki, a rural area of South Africa with a population of 150,000 serviced by 1 hospital and 12 clinics, Médecins Sans Frontières has been supporting a program to deliver human immunodeficiency virus (HIV) services through decentralization to primary health care clinics, task shifting (including nurse-initiated as opposed to physician-initiated treatment), and community support. This approach has allowed for a rapid scale-up of treatment with satisfactory outcomes. Although the general approach in South Africa is to provide ART through hospitals-which seriously limits access for many people, if not the majority of people-1-year outcomes in Lusikisiki are comparable in the clinics and hospital. The greater proximity and acceptability of services at the clinic level has led to a faster enrollment of people into treatment and better retention of patients in treatment (2% vs. 19% lost to follow-up). In all, 2200 people were receiving ART in Lusikisiki in 2006, which represents 95% coverage. Maintaining quality and coverage will require increased resource input from the public sector and full acceptance of creative approaches to implementation, including task shifting and community involvement

Extending holographic LEED to ordered small unit cell superstructures

Following on the success of the recent application of holographic LEED to the determination of the 3D atomic geometry of Si adatoms on a SiC(111) p(3x3) surface, which enabled that structure to be solved, we show in this paper that a similar technique allows the direct recovery of the local geometry of adsorbates forming superstructures as small as p(2x2), even in the presence of a local substrate reconstruction.Comment: 10 pages, 5 figures postscript included, revtex, Phys. Rev. B in pres

First-principles embedded-cluster calculations of the neutral and charged oxygen vacancy at the rutile TiO₂(110) surface

We perform full-potential screened-hybrid density-functional theory calculations to compare the thermodynamic stability of neutral and charged states of the surface oxygen vacancy at the rutile TiO2(110) surface. Solid-state (QM/MM) embedded-cluster calculations are employed to account for the strong TiO2 polarization response to the charged defect states. Similarly to the situation for the bulk O vacancy, the +2 charge state VO2+ is found to be energetically by far the most stable. Only for Fermi-level positions very close to the conduction band, small polarons may at best be trapped by the charged vacancy. The large decrease in the VO2+ formation energy with decreasing Fermi-level position indicates strongly enhanced surface O vacancy concentrations for p-doped samples

Transferable ionic parameters for first-principles Poisson-Boltzmann solvation calculations: Neutral solutes in aqueous monovalent salt solutions

Implicit solvation calculations based on a Stern-layer corrected size-modified Poisson-Boltzmann (SMPB) model are an effective approach to capture electrolytic effects in first-principles electronic structure calculations. For a given salt solution, they require a range of ion-specific parameters, which describe the size of the dissolved ions as well as thickness and shape of the Stern layer. Out of this defined parameter space, we show that the Stern layer thickness expressed in terms of the solute’s electron density and the resulting ionic cavity volume completely determine ion effects on the stability of neutral solutes. Using the efficient SMPB functionality of the full-potential density-functional theory package FHI-aims, we derive optimized such Stern layer parameters for neutral solutes in various aqueous monovalent electrolytes. The parametrization protocol relies on fitting to reference Setschenow coefficients that describe solvation free energy changes with ionic strength at low to medium concentrations. The availability of such data for NaCl solutions yields a highly predictive SMPB model that allows to recover the measured Setschenow coefficients with an accuracy that is comparable to prevalent quantitative regression models. Correspondingly derived SMPB parameters for other salts suffer from a much scarcer experimental data base but lead to Stern layer properties that follow a physically reasonable trend with ionic hydration numbers

First-Principles Free-Energy Barriers for Photoelectrochemical Surface Reactions: Proton Abstraction at TiO₂(110)

We explicitly calculate the free-energy barrier for the initial proton abstraction in the water splitting reaction at rutile TiO2(110) through ab initio molecular dynamics. Combining solid-state embedding, an energy based reaction coordinate and state-of-the-art free-energy reconstruction techniques renders the calculation tractable at the hybrid density-functional theory level. The obtained free-energy barrier of approximately 0.2 eV, depending slightly on the orientation of the first acceptor water molecule, suggests a hindered reaction on the pristine rutile surface

Thermal and electronic fluctuations of flexible adsorbed molecules : azobenzene on Ag(111)

We investigate the thermal and electronic collective fluctuations that contribute to the finite-temperature adsorption properties of flexible adsorbates on surfaces on the example of the molecular switch azobenzene C12H10N2 on the Ag(111) surface. Using first-principles molecular dynamics simulations, we obtain the free energy of adsorption that accurately accounts for entropic contributions, whereas the inclusion of many-body dispersion interactions accounts for the electronic correlations that govern the adsorbate binding. We find the adsorbate properties to be strongly entropy driven, as can be judged by a kinetic molecular desorption prefactor of 10^24 s−1 that largely exceeds previously reported estimates. We relate this effect to sizable fluctuations across structural and electronic observables. A comparison of our calculations to temperature-programed desorption measurements demonstrates that finite-temperature effects play a dominant role for flexible molecules in contact with polarizable surfaces, and that recently developed first-principles methods offer an optimal tool to reveal novel collective behavior in such complex systems

Plastic-crystalline solid-state electrolytes: Ionic conductivity and orientational dynamics in nitrile mixtures

Many plastic crystals, molecular solids with long-range, center-of-mass crystalline order but dynamic disorder of the molecular orientations, are known to exhibit exceptionally high ionic conductivity. This makes them promising candidates for applications as solid-state electrolytes, e.g., in batteries. Interestingly, it was found that the mixing of two different plastic-crystalline materials can considerably enhance the ionic dc conductivity, an important benchmark quantity for electrochemical applications. An example is the admixture of different nitriles to succinonitrile, the latter being one of the most prominent plastic-crystalline ionic conductors. However, until now only few such mixtures were studied. In the present work, we investigate succinonitrile mixed with malononitrile, adiponitrile, and pimelonitrile, to which 1 mol% of Li ions were added. Using differential scanning calorimetry and dielectric spectroscopy, we examine the phase behavior and the dipolar and ionic dynamics of these systems. We especially address the mixing-induced enhancement of the ionic conductivity and the coupling of the translational ionic mobility to the molecular reorientational dynamics, probably arising via a "revolving-door" mechanism.Comment: 9 pages, 7 figures; revised version as accepted for publication in J. Chem. Phy

Gluon Condensation in Nonperturbative Flow Equations

We employ nonperturbative flow equations for an investigation of the effective action in Yang-Mills theories. We compute the effective action $\Gamma[B]$ for constant color magnetic fields $B$ and examine Savvidy's conjecture of an unstable perturbative vacuum. Our results indicate that the absolute minimum of $\Gamma[B]$ occurs for B=0. Gluon condensation is described by a nonvanishing expectation value of the regularized composite operator $F_{\mu\nu}F^{\mu\nu}$ which agrees with phenomenological estimates.Comment: 64 pages, late