Mesoscale heat waves induced by orography

This work is devoted to the analysis of an unusual and sudden thermal fluctuation that interested portions of Friuli Venezia Giulia (Italy) during the night of 27 July 1983. The whole 1983 summer was extremely warm in Europe and in particular on the Italian peninsula, from the Alps down to Sicily. Nevertheless, the day of 27 July 1983 in Friuli Venezia Giulia deserves special attention because the observed maximum temperatures did not occur during day-time but during night-time (from 23:00 up to 24:00 LT, 21:00–22:00 UTC). Peaks of 34.8°C and values of relative humidity of the order of 28% were registered by the official network of weather stations. This event interested mainly the central-eastern part of the plain of Friuli Venezia Giulia, a few kilometers far from the Slovenian border and relieves. The thermal anomalies lasted up to an hour, then temperatures decreased toward values more usual for the climate of the month. The study of this event is carried out with the aid of the AR-WRF numerical atmospheric model, initialized through the ECMWF analysis. The numerical simulations highlight the important role played by orography, jointly with the peculiar thermal structure of the atmosphere, for the enhancing of the internal wave pattern over that area. According to the sensitivity studies realized, the amplification of the internal wave pattern might represent a possible explanation for that meteorological enigma

Negative heat capacity of small systems in the microcanonical ensemble

We propose a new mechanism to explain the origin of negative heat capacity in small systems. We show how a particular structure of the potential energy surface combined with a microcanonical treatment results in negative heat capacity. Moreover, this effect occurs under true equilibrium conditions. An energy landscape with a sudden and spatially large opening leads to a negative heat capacity. The magnitude of this effect is related to the extent of the opening and the number of particles in the system

The ice-vapor interface and the melting point of ice Ih for the polarizable POL3 water model

International audienceWe use molecular dynamics simulations to determine the melting point of ice Ih for the polarizable POL3 water force field (Dang, L. X. J. Chem. Phys.1992, 97, 2659). Simulations are performed on a slab of ice Ih with two free surfaces at several different temperatures. The analysis of the time evolution of the total energy in the course of the simulations at the set of temperatures yields the melting point of the POL3 model to be Tm = 180 ± 10 K. Moreover, the results of the simulations show that the degree of hydrogen-bond disorder occurring in the bulk of POL3 ice is larger (at the corresponding degree of undercooling) than in ice modeled by nonpolarizable water models. These results demonstrate that the POL3 water force field is rather a poor model for studying ice and ice−liquid or ice−vapor interfaces. While a number of polarizable water models have been developed over the past years, little is known about their performance in simulations of supercooled water and ice. This study thus highlights the need for testing of the existing polarizable water models over a broad range of temperatures, pressures, and phases, and developing a new polarizable water force field, reliable over larger areas of the phase diagram

Molecular simulation studies of the adsorption of nitrate on the surface of ice

International audienc

Designing High-Affinity Peptides for Organic Molecules by Explicit Solvent Molecular Dynamics

Financial support from the grant \u201cAssociazione Italiana per la Ricerca sul Cancro 5 per mille, Rif. 12214 \u201d, and \u201cFondo per gli Investimenti della Ricerca di Base-Accordo di programma, Rif. RBAP11ETKA\u201d

Reply to “Comment on ‘Liquid-Gas Interface of Iron Aqueous Solutions and Fenton Reagents’”

A Viewpoint regarding our recently published Letter in this Journal (Gladich et al. J. Phys. Chem. Lett. 13, 2994–3001) criticizes some of our conclusions. While a sentence in the abstract and one in the conclusion of the Letter might seem too conclusive, in the body text we objectively discussed experimental results obtained by means of three different surface-/interface-sensitive spectroscopies. Such results were supported by theoretical calculations. The aim of our work was not to criticize past results. On the contrary, we critically discussed our data taking into account those obtained in the past

Computational Evolution Protocol for Peptide Design

Computational peptide design is useful for therapeutics, diagnostics, and vaccine development. To select the most promising peptide candidates, the key is describing accurately the peptide-target interactions at the molecular level. We here review a computational peptide design protocol whose key feature is the use of all-atom explicit solvent molecular dynamics for describing the different peptide-target complexes explored during the optimization. We describe the milestones behind the development of this protocol, which is now implemented in an open-source code called PARCE. We provide a basic tutorial to run the code for an antibody fragment design example. Finally, we describe three additional applications of the method to design peptides for different targets, illustrating the broad scope of the proposed approach

Liquid-Gas Interface of Iron Aqueous Solutions and Fenton Reagents

Fenton chemistry, involving the reaction between Fe2+ and hydrogen peroxide, is well-known due to its applications in the mineralization of extremely stable molecules. Different mechanisms, influenced by the reaction conditions and the solvation sphere of iron ions, influence the fate of such reactions. Despite the huge amount of effort spent investigating such processes, a complete understanding is still lacking. This work combines photoelectron spectroscopy and theoretical calculations to investigate the solvation and reactivity of Fe2+ and Fe3+ ions in aqueous solutions. The reaction with hydrogen peroxide, both in homogeneous Fenton reagents and at the liquid–vapor interface, illustrates that both ions are homogeneously distributed in solutions and exhibit an asymmetric octahedral coordination to water in the case of Fe2+. No indications of differences in the reaction mechanism between the liquid–vapor interface and the bulk of the solutions have been found, suggesting that Fe3+ and hydroxyl radicals are the only intermediates

A review of air-ice chemical and physical interactions (AICI): liquids, quasi liquids, and solids in snow

Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed