Crystal structure of barium oxonitridophosphate, Ba3P6O6N8

Ba3N8O6P6, trigonal, P3 (no. 147), a = 7.40227(9) Å, c = 6.3144(1) Å, V = 299.6 Å3, Z = 1, R(I) = 0.008, R(P) = 0.041, T = 297(2) K

Renormalization of myoglobin-ligand binding energetics by quantum many-body effects

We carry out a first-principles atomistic study of the electronic mechanisms of ligand binding and discrimination in the myoglobin protein. Electronic correlation effects are taken into account using one of the most advanced methods currently available, namely a linear-scaling density functional theory (DFT) approach wherein the treatment of localized iron 3d electrons is further refined using dynamical mean-field theory (DMFT). This combination of methods explicitly accounts for dynamical and multi-reference quantum physics, such as valence and spin fluctuations, of the 3d electrons, whilst treating a significant proportion of the protein (more than 1000 atoms) with density functional theory. The computed electronic structure of the myoglobin complexes and the nature of the Fe-O2 bonding are validated against experimental spectroscopic observables. We elucidate and solve a long standing problem related to the quantum-mechanical description of the respiration process, namely that DFT calculations predict a strong imbalance between O2 and CO binding, favoring the latter to an unphysically large extent. We show that the explicit inclusion of many body-effects induced by the Hund's coupling mechanism results in the correct prediction of similar binding energies for oxy- and carbonmonoxymyoglobin.Comment: 7 pages, 5 figures. Accepted for publication in the Proceedings of the National Academy of Sciences of the United States of America (2014). For the published article see http://www.pnas.org/content/early/2014/04/09/1322966111.abstrac

Synthesis of satellite (MODIS), aircraft (ICARTT), and surface (IMPROVE, EPA-AQS, AERONET) aerosol observations over eastern North America to improve MODIS aerosol retrievals and constrain surface aerosol concentrations and sources

We use an ensemble of satellite (MODIS), aircraft, and ground-based aerosol observations during the ICARTT field campaign over eastern North America in summer 2004 to (1) examine the consistency between different aerosol measurements, (2) evaluate a new retrieval of aerosol optical depths (AODs) and inferred surface aerosol concentrations (PM2.5) from the MODIS satellite instrument, and (3) apply this collective information to improve our understanding of aerosol sources. The GEOS-Chem global chemical transport model (CTM) provides a transfer platform between the different data sets, allowing us to evaluate the consistency between different aerosol parameters observed at different times and locations. We use an improved MODIS AOD retrieval based on locally derived visible surface reflectances and aerosol properties calculated from GEOS-Chem. Use of GEOS-Chem aerosol optical properties in the MODIS retrieval not only results in an improved AOD product but also allows quantitative evaluation of model aerosol mass from the comparison of simulated and observed AODs. The aircraft measurements show narrower aerosol size distributions than those usually assumed in models, and this has important implications for AOD retrievals. Our MODIS AOD retrieval compares well to the ground-based AERONET data (R = 0.84, slope = 1.02), significantly improving on the MODIS c005 operational product. Inference of surface PM2.5 from our MODIS AOD retrieval shows good correlation to the EPA-AQS data (R = 0.78) but a high regression slope (slope = 1.48). The high slope is seen in all AOD-inferred PM2.5 concentrations (AERONET: slope = 2.04; MODIS c005: slope = 1.51) and could reflect a clear-sky bias in the AOD observations. The ensemble of MODIS, aircraft, and surface data are consistent in pointing to a model overestimate of sulfate in the mid-Atlantic and an underestimate of organic and dust aerosol in the southeastern United States. The sulfate overestimate could reflect an excessive contribution from aqueous-phase production in clouds, while the organic carbon underestimate could possibly be resolved by a new secondary pathway involving dicarbonyls

Surface diffusion in catalysts probed by APGSTE NMR

In this work we report the application of a recently developed experimental protocol using Pulsed Field Gradient (PFG) Nuclear Magnetic Resonance (NMR) techniques to simultaneously assess bulk pore and surface diffusion coefficients in liquid saturated porous catalysts. This method has been developed to study solvent effects on the diffusion of methyl ethyl ketone (MEK) in mesoporous 1 wt% Pd/Al2O3 catalyst trilobes. The selection of solvents used in this work is known to have a complex effect on reaction rates and hence catalyst performance in heterogeneous liquid phase catalysis. Here, we report the bulk pore and surface diffusion characteristics of MEK, water and isopropyl alcohol (IPA) in 1 wt% Pd/Al2O3 catalyst trilobes. The results show that the physicochemical interactions of molecules in the porous catalyst matrix are very different for the different molecules. We also find that the mobility of water appears to be affected strongest by the catalyst surface

Declarative Modeling–An Academic Dream or the Future for BPM?

Declarative modeling has attracted much attention over the last years, resulting in the development of several academic declarative modeling techniques and tools. The absence of empirical evaluations on their use and usefulness, however, raises the question whether practitioners are attracted to using those techniques. In this paper, we present a study on what practitioners think of declarative modeling. We show that the practitioners we involved in this study are receptive to the idea of a hybrid approach combining imperative and declarative techniques, rather than making a full shift from the imperative to the declarative paradigm. Moreover, we report on requirements, use cases, limitations, and tool support of such a hybrid approach. Based on the gained insight, we propose a research agenda for the development of this novel modeling approach

Flipping the Classroom to Train Citizen Scientists in Invasive Species Detection and Response

Extension educators are increasingly using flipped classrooms, wherein online content delivery precedes in-person learning. We have applied this approach to two Extension programs in which citizen scientists are trained in early detection of invasive species. Our goal in using the tool of flipped classrooms is to accommodate large amounts of content while focusing classroom time on skills development. In 2017, we assessed efficacy of the flipped classroom through knowledge tests and surveys completed by 174 participants and 106 participants, respectively. Results demonstrated large knowledge gains and high participant satisfaction. We encourage Extension professionals to consider whether use of the flipped classroom format could advance achievement of their programs\u27 learning objectives

Permeation of CO₂ and N₂ through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions

Glassy polymers are often used for gas separations because of their high selectivity. Although the dual‐mode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reaction–diffusion modeling to characterize the time‐dependent permeation of N₂ and CO₂ through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental time‐dependent permeation data for both gases in the presteady‐state and steady‐state regimes show that both single‐ and dual‐mode reaction–diffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environment‐sensitive diffusion coefficients as a vital characteristic of transport in glassy polymers