Proton transport in doped yttrium oxide. Monte-Carlo simulation

The Monte-Carlo technique is used to calculate the dependences of the tracer diffusion coefficient D* and conductivity ?? of protons on the temperature and content x of the acceptor dopant in oxides with the structure of distorted fluorite (??bixbyite?? structure). Analysis is carried out for the calcium doped Y₂O₃ oxide as an example. The effect of dopant-generated traps (different energy states for protons) and also the effect of site blocking due to interaction of protons between themselves and with oxygen vacancies are considered. It is shown that mobility of protons decreases significantly as a result of doping already at low x ?? 1 mol %. The behavior of conductivity noticeably depends on the distribution of dopant ions over nonequivalent cation sites in the lattice. The predominant dopant distribution over the sites of the same type accounts for the appearance of a maximum in the dependence of ??(x) when correlations are taken into account.     

Random replicators with high-order interactions

We use tools of the equilibrium statistical mechanics of disordered systems to study analytically the statistical properties of an ecosystem composed of N species interacting via random mutual interactions, as well as via deterministic self-interactions of order p>/=2. We show that the main effect of increasing the order of the interactions among the species is to make the system less competitive, in the sense that the fraction of extinct species is greatly reduced. In addition, we find that for p>2 there is a threshold value which gives a lower bound to the concentration of the surviving species, preventing then the existence of rare species and, consequently, increasing the robustness of the ecosystem to external perturbations.     

Coexistence of self-organized criticality and intermittent turbulence in the solar corona

An extended data set of extreme ultraviolet images of the solar corona provided by the SOHO spacecraft is analyzed using statistical methods common to studies of self-organized criticality (SOC) and intermittent turbulence (IT). The data exhibit simultaneous hallmarks of both regimes: namely, power-law avalanche statistics as well as multiscaling of structure functions for spatial activity. This implies that both SOC and IT may be manifestations of a single complex dynamical process entangling avalanches of magnetic energy dissipation with turbulent particle flows.     

Maturation of auditory temporal integration and inhibition assessed with event-related potentials (ERPs)

Background

We examined development of auditory temporal integration and inhibition by assessing electrophysiological responses to tone pairs separated by interstimulus intervals (ISIs) of 25, 50, 100, 200, 400, and 800 ms in 28 children aged 7 to 9 years, and 15 adults.

Results

In adults a distinct neural response was elicited to tones presented at ISIs of 25 ms or longer, whereas in children this was only seen in response to tones presented at ISIs above 100 ms. In adults, late N1 amplitude was larger for the second tone of the tone pair when separated by ISIs as short as 100 ms, consistent with the perceptual integration of successive stimuli within the temporal window of integration. In contrast, children showed enhanced negativity only when tone pairs were separated by ISIs of 200 ms. In children, the amplitude of the P1 component was attenuated at ISIs below 200 ms, consistent with a refractory process.

Conclusions

These results indicate that adults integrate sequential auditory information into smaller temporal segments than children. These results suggest that there are marked maturational changes from childhood to adulthood in the perceptual processes underpinning the grouping of incoming auditory sensory information, and that electrophysiological measures provide a sensitive, non-invasive method allowing further examination of these changes.     

Stepwise Versus Concerted Mechanisms in General‐Base Catalysis by Serine Proteases

General‐base catalysis in serine proteases still poses mechanistic challenges despite decades of research. Whether proton transfer from the catalytic Ser to His and nucleophilic attack on the substrate are concerted or stepwise is still under debate, even for the classical Asp‐His‐Ser catalytic triad. To address these key catalytic steps, the transformation of the Michaelis complex to tetrahedral complex in the covalent inhibition of two prototype serine proteases was studied: chymotrypsin (with the catalytic triad) inhibition by a peptidyl trifluoromethane and GlpG rhomboid (with Ser‐His dyad) inhibition by an isocoumarin derivative. The sampled MD trajectories of averaged pK_a values of catalytic residues were QM calculated by the MD‐QM/SCRF(VS) method on molecular clusters simulating the active site. Differences between concerted and stepwise mechanisms are controlled by the dynamically changing pK_a values of the catalytic residues as a function of their progressively reduced water exposure, caused by the incoming ligand.     

Role of an acceptor impurity in the proton transfer in proton-conducting oxides

The influence of interaction of protons with defects (acceptor impurities, oxygen vacancies) and with each other on the proton transfer in acceptor-doped proton-conducting oxides A ^II B _1?x ^IV R _x ^III O_{3 ? δ} with the perovskite structure and in oxides A _2?x ^III R _x ^II O_{3 ? δ} with the structure of a distorted fluorite (bixbyite) has been investigated theoretically. The tracer diffusion coefficient D* and proton mobility have been calculated by the Monte Carlo method and analytically. It has been shown that the interaction of protons with defects substantially affects the magnitude and behavior of the transfer coefficients. The interaction with acceptor impurities plays the most important role. The proton mobility significantly decreases even at a low dopant concentration (x ～ 1–3 at %). The dependence of the proton conductivity σ on the impurity concentration can exhibit maxima. For oxides with the bixbyite structure including nonequivalent cation sites, the distribution of the dopant over these sites has a strong influence on the dependence σ(x). The obtained results have been used to interpret the experimental data on the proton conductivity for a number of oxides.     

Mobility and diffusion of oxygen isotopes in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6+<Emphasis Type="Italic">x</Emphasis></Subscript>: Monte carlo simulation

The self-diffusion (D₀) and isotope diffusion (D*) coefficients of oxygen in YBa₂Cu₃O_6+x are calculated as functions of the temperature (600–1200 K) and the oxygen content (0<x<1). The Monte Carlo simulation is performed with due regard for both the interaction of oxygen ions at lattice sites in the basal planes of YBa₂Cu₃O_6+x and the interaction between a jumping ion at a saddle point and the environment. Equilibrium thermodynamic characteristics (including the phase diagram and the heat capacity) are calculated in terms of the Hamiltonian of interaction between oxygen ions at the lattice sites. It is found that an increase in the oxygen content leads to a decrease in the diffusion coefficients D₀ and D*, an increase in the effective activation energies for diffusion by 0.3–0.5 eV, and a decrease in the Haven ratio from 1 to ～0.5.