Representations and descriptors unifying the study of molecular and bulk systems

Establishing a unified framework for describing the structures of molecular and periodic systems is a long-standing challenge in physics, chemistry, and material science. With the rise of machine learning methods in these fields, there is a growing need for such a method. This perspective aims to discuss the development and use of three promising approaches-topological, atom-density, and symmetry-based-for the prediction and rationalization of physical, chemical, and mechanical properties of atomistic systems across different scales and compositions

Mechanism of Molybdenum-Mediated Carbon Monoxide Deoxygenation and Coupling: Mono- and Dicarbyne Complexes Precede C–O Bond Cleavage and C–C Bond Formation

Deoxygenative coupling of CO to value-added C_(≥2) products is challenging and mechanistically poorly understood. Herein, we report a mechanistic investigation into the reductive coupling of CO, which provides new fundamental insights into a multielectron bond-breaking and bond-making transformation. In our studies, the formation of a bis(siloxycarbyne) complex precedes C–O bond cleavage. At −78 °C, over days, C–C coupling occurs without C–O cleavage. However, upon warming to 0 °C, C–O cleavage is observed from this bis(siloxycarbyne) complex. A siloxycarbyne/CO species undergoes C–O bond cleavage at lower temperatures, indicating that monosilylation, and a more electron-rich Mo center, favors deoxygenative pathways. From the bis(siloxycarbyne), isotopic labeling experiments and kinetics are consistent with a mechanism involving unimolecular silyl loss or C–O cleavage as rate-determining steps toward carbide formation. Reduction of Mo(IV) CO adducts of carbide and silylcarbyne species allowed for the spectroscopic detection of reduced silylcarbyne/CO and mixed silylcarbyne/siloxycarbyne complexes, respectively. Upon warming, both of these silylcarbynes undergo C–C bond formation, releasing silylated C_2O_1 fragments and demonstrating that the multiple bonded terminal Mo≡C moiety is an intermediate on the path to deoxygenated, C–C coupled products. The electronic structures of Mo carbide and carbyne species were investigated quantum mechanically. Overall, the present studies establish the elementary reactions steps by which CO is cleaved and coupled at a single metal site

Wetting and contact-line effects for spherical and cylindrical droplets on graphene layers: A comparative molecular-dynamics investigation

In Molecular Dynamics (MD) simulations, interactions between water molecules and graphitic surfaces are often modeled as a simple Lennard-Jones potential between oxygen and carbon atoms. A possible method for tuning this parameter consists of simulating a water nanodroplet on a flat graphitic surface, measuring the equilibrium contact angle, extrapolating it to the limit of a macroscopic droplet and finally matching this quantity to experimental results. Considering recent evidence demonstrating that the contact angle of water on a graphitic plane is much higher than what was previously reported, we estimate the oxygen-carbon interaction for the recent SPC/Fwwater model. Results indicate a value of about 0.2 kJ/mol, much lower than previous estimations. We then perform simulations of cylindrical water filaments on graphitic surfaces, in order to compare and correlate contact angles resulting from these two different systems. Results suggest that modified Young's equation does not describe the relation between contact angle and drop size in the case of extremely small systems and that contributions different from the one deriving from contact line tension should be taken into account.Comment: To be published on Physical Review E (http://pre.aps.org/

The Radio Afterglow and Host Galaxy of the Dark GRB 020819

Of the fourteen gamma-ray bursts (GRBs) localized to better than 2' radius with the SXC on HETE-2, only two lack optical afterglow detections, and the high recovery rate among this sample has been used to argue that the fraction of truly dark bursts is ~10%. While a large fraction of earlier dark bursts can be explained by the failure of ground-based searches to reach appropriate limiting magnitudes, suppression of the optical light of these SXC dark bursts seems likely. Here we report the discovery and observation of the radio afterglow of GRB 020819, an SXC dark burst, which enables us to identify the likely host galaxy (probability of 99.2%) and hence the redshift (z=0.41) of the GRB. The radio light curve is qualitatively similar to that of several other radio afterglows, and may include an early-time contribution from the emission of the reverse shock. The proposed host is a bright R = 19.5 mag barred spiral galaxy, with a faint R ~ 24.0 mag "blob'' of emission, 3" from the galaxy core (16 kpc in projection), that is coincident with the radio afterglow. Optical photometry of the galaxy and blob, beginning 3 hours after the burst and extending over more than 100 days, establishes strong upper limits to the optical brightness of any afterglow or associated supernova. Combining the afterglow radio fluxes and our earliest R-band limit, we find that the most likely afterglow model invokes a spherical expansion into a constant-density (rather than stellar wind-like) external environment; within the context of this model, a modest local extinction of A_V ~ 1 mag is sufficient to suppress the optical flux below our limits.Comment: 7 pages, 2 figures. ApJ, in press. For more info on dark bursts, see http://www.astro.ku.dk/~pallja/dark.htm

Examining Visual Field Loss in Patients in Glaucoma Clinics During Their Predicted Remaining Lifetime

Purpose.: To evaluate the proportion of patients in glaucoma clinics progressing at rates that would result in visual disability within their expected lifetime. Methods.: This retrospective study used visual field (VF) series of at least 3 years’ duration from 3790 UK patients in glaucoma clinics calculating rates of loss for each eye using linear regression of mean deviation (MD) over time. Residual life expectancies derived from the UK Office of National Statistics actuarial tables for each patient were combined with these rates to estimate predicted MDs at end of expected lifetime. The proportion of patients projected to progress to visual impairment (MD: −14 dB or worse) or statutory blindness (MD: −22 dB or worse) in both eyes before end of expected lifetime was calculated. Results.: Only 3.0% (95% confidence interval [CI] 2.7%–3.4%) of patient eyes progressed at faster than −1.5 dB/year (n = 7149 eyes). Of those patients with both eyes followed, 5.2% (CI 4.5%–6.0%) were predicted to progress to statutory blindness, with a further 10.4% (CI 9.4%–11.4%) reaching visual impairment in their lifetime. More than 90% (CI 85.7%–94.3%) of patients predicted to progress to statutory blindness, had an MD worse than −6 dB in at least one eye at presentation. Conclusions.: This modeling exercise indicates that most patients in glaucoma clinics are not at high risk of progressing to statutory blindness. The likelihood of patients suffering impairment in their lifetimes is linked to VF loss at presentation, which illuminates the importance of reliably detecting significant VF defects in primary care

The Open Access Advantage Revisited

This paper is a revision of one that appeared in 2008, incorporating the many developments and changes that have happened since then.published_or_final_versio

The Open Access Advantage

Hong Kong Open Access Committeepublished_or_final_versio

Electronic Structure of Few-Layer Graphene: Experimental Demonstration of Strong Dependence on Stacking Sequence

The electronic structure of few-layer graphene (FLG) samples with crystalline order was investigated experimentally by infrared absorption spectroscopy for photon energies ranging from 0.2 - 1 eV. Distinct optical conductivity spectra were observed for different samples having precisely the same number of layers. The different spectra arise from the existence of two stable polytypes of FLG, namely, Bernal (AB) stacking and rhombohedral (ABC) stacking. The observed absorption features, reflecting the underlying symmetry of the two polytypes and the nature of the associated van Hone singularities, were reproduced by explicit calculations within a tight-binding model. The findings demonstrate the pronounced effect of stacking order on the electronic structure of FLG.Comment: 13 pages, 3 figure

A practical approach to the sensitivity analysis for kinetic Monte Carlo simulation of heterogeneous catalysis

Lattice kinetic Monte Carlo simulations have become a vital tool for predictive quality atomistic understanding of complex surface chemical reaction kinetics over a wide range of reaction conditions. In order to expand their practical value in terms of giving guidelines for the atomic level design of catalytic systems, it is very desirable to readily evaluate a sensitivity analysis for a given model. The result of such a sensitivity analysis quantitatively expresses the dependency of the turnover frequency, being the main output variable, on the rate constants entering the model. In the past, the application of sensitivity analysis, such as degree of rate control, has been hampered by its exuberant computational effort required to accurately sample numerical derivatives of a property that is obtained from a stochastic simulation method. In this study, we present an efficient and robust three-stage approach that is capable of reliably evaluating the sensitivity measures for stiff microkinetic models as we demonstrate using the CO oxidation on RuO2(110) as a prototypical reaction. In the first step, we utilize the Fisher information matrix for filtering out elementary processes which only yield negligible sensitivity. Then we employ an estimator based on the linear response theory for calculating the sensitivity measure for non- critical conditions which covers the majority of cases. Finally, we adapt a method for sampling coupled finite differences for evaluating the sensitivity measure for lattice based models. This allows for an efficient evaluation even in critical regions near a second order phase transition that are hitherto difficult to control. The combined approach leads to significant computational savings over straightforward numerical derivatives and should aid in accelerating the nano-scale design of heterogeneous catalysts

Size fractionation of trace elements in the surface water and groundwater of the Ganjiang River and Xiushui River basins, China

The research of trace element behaviour and size fractionation is significant to understand the processes in the water-rock system. Moreover, the aqueous speciation of trace elements is strongly related to their distribution and toxicity. In this research, trace elements behaviour and their size fractionation are investigated in the natural water (the surface water and shallow groundwater) of the Ganjiang River and Xiushui River basins. Trace element concentrations were measured by ICP-MS. The authors estimated the size fractionation of the trace elements between suspended forms (>0.45 [mu]m) and dissolved fractions, which included truly dissolved (1 kDa) and colloidal particles (0.45 [mu]m-1 kDa)), after filtration through a 0.45 [mu]m acetate cellulose membrane filter. The distinct features of the trace element size fractionation were identified. The size fractionation of the trace elements under different conditions (in the surface water and shallow groundwater) was studied