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It is worth understanding the potentials of zero charge (PZCs) and structures of stepped metal/water interfaces, because for many electrocatalytic reactions, stepped surfaces are more active than atomically flat surfaces. Herein, a series of stepped Pt/water interfaces are modeled at different step densities with ab initio molecular dynamics. It is found that the structures of Pt/water interfaces are significantly influenced by the step density, particularly in regard to the distribution of chemisorbed water. The step sites of metal surfaces are more preferred for water chemisorption than terrace sites, and until the step density is very low, water will chemisorb on the terrace. In addition, it is revealed that the PZCs of stepped Pt/water interfaces are generally smaller than that of Pt(111), and the difference is mainly attributed to the difference in their work function, providing a simple way to estimate the PZCs of stepped metal surfaces. Finally, it is interesting to see that the Volta potential difference is almost the same for Pt/water interfaces with different step densities, although their interface structures and magnitude of charge transfer clearly differ. [ABSTRACT FROM AUTHOR]

The two-parameter Weibull distribution has been widely adopted to model the lifetime statistics of dielectric breakdown under constant voltage, but recent lifetime testing for high-k gate dielectrics has revealed a systematic departure from Weibull statistics, evocative of lifetime statistics for small quasibrittle structures under constant stress. Here we identify a mathematical analogy between the dielectric breakdown in semiconductor electronic devices and the finite-size weakest-link model for mechanical strength of quasibrittle structures and adapt a recently developed probabilistic theory of structural failure to gate dielectrics. Although the theory is general and does not rely on any particular model of local breakdown events, we show how its key assumptions can be derived from the classical dielectric breakdown model, which predicts certain scaling exponents. The theory accurately fits the observed kinked shape of the histograms of lifetime plotted in Weibull scale, as well as the measured dependence of the median lifetime on the gate area (or size), including its deviation from a power law. The theory also predicts that the Weibull modulus for breakdown lifetime increases in proportion to the thickness of the oxide layer and suggests new ideas for more effective reliability testing. [ABSTRACT FROM AUTHOR]

Unraveling the origin of Helmholtz capacitance is of paramount importance for understanding the interfacial structure and electrostatic potential distribution of electric double layers (EDL). In this work, we combined the methods of ab initio molecular dynamics and classical molecular dynamics and modeled electrified Cu(100)/electrolyte and graphene/electrolyte interfaces for comparison. It was proposed that the Helmholtz capacitance is composed of three parts connected in series: the usual solvent capacitance, water chemisorption induced capacitance, and Pauling repulsion caused gap capacitance. We found the Helmholtz capacitance of graphene is significantly lower than that of Cu(100), which was attributed to two intrinsic factors. One is that graphene has a wider gap layer at interface, and the other is that graphene is less active for water chemisorption. Finally, based on our findings, we provide suggestions for how to increase the EDL capacitance of graphene-based materials in future work, and we also suggest that the new understanding of the potential distribution across the Helmholtz layer may help explain some experimental phenomena of electrocatalysis. [ABSTRACT FROM AUTHOR]