Structure of the Hexadecane Rotator Phase: Combination of X-ray Spectra and Molecular Dynamics Simulation.

Rotator phases are rotationally disordered plastic crystals, some of which can form upon freezing of alkane at alkane-water interfaces. Existing X-ray diffraction studies show only partial unit cell information for rotator phases of some alkanes. This includes the rotator phase of n-hexadecane, which is a transient metastable phase in pure alkane systems, but shows remarkable stability at interfaces when mediated by a surfactant. Here, we combine synchrotron X-ray diffraction data and molecular dynamics (MD) simulations, reporting clear evidence of the face-centered orthorhombic RI rotator phase from spectra for two hexadecane emulsions, one stabilized by Brij C10 and another by Tween 40 surfactants. MD simulations of pure hexadecane use the recently developed Williams 7B force field, which is capable of reproducing crystal-to-rotator phase transitions, and it also predicts the crystal structure of the RI phase. Full unit cell information is obtained by combining unit cell dimensions from synchrotron data and molecular orientations from MD simulations. A unit cell model of the RI phase is produced in the crystallographic information file (CIF) format, with each molecule represented by a superposition of four rotational positions, each with 25% occupancy. Powder diffraction spectra computed using this model are in good agreement with the experimental spectra

Benchmarking of Molecular Dynamics Force Fields for Solid-Liquid and Solid-Solid Phase Transitions in Alkanes

Accurate prediction of alkane phase transitions involving solids is needed to prevent catastrophic pipeline blockages, improve lubrication formulations, smart insulation, and energy storage, as well as bring fundamental understanding to processes such as artificial morphogenesis. However, simulation of these transitions is challenging and therefore often omitted in force field development. Here, we perform a series of benchmarks on seven representative molecular dynamics models (TraPPE, PYS, CHARMM36, L-OPLS, COMPASS, Williams, and the newly optimized Williams 7B), comparing with experimental data for liquid properties, liquid-solid, and solid-solid phase transitions of two prototypical alkanes, n-pentadecane (C15) and n-hexadecane (C16). We find that existing models overestimate the melting points by up to 34 K, with PYS and Williams 7B yielding the most accurate results deviating only 2 and 3 K from the experiment. We specially design order parameters to identify crystal-rotator phase transitions in alkanes. United-atom models could only produce a rotator phase with complete rotational disorder, whereas all-atom models using a 12-6 Lennard-Jones potential show no rotator phase even when superheated above the melting point. In contrast, Williams (Buckingham potential) and COMPASS (9-6 Lennard-Jones) reproduce the crystal-to-rotator phase transition, with the optimized Williams 7B model having the most accurate crystal-rotator transition temperature of C15.</p

Spin States of Homochiral and Heterochiral Isomers of [Fe(PyBox)2]2+ Derivatives

The following iron(II) complexes of 2,6-bis(oxazolinyl)pyridine (PyBox; LH) derivatives are reported: [Fe(LH)2][ClO4]2 (1); [Fe((R)-LMe)2][ClO4]2 ((R)-2; LMe=2,6-bis{4-methyloxazolinyl}pyridine); [Fe((R)-LPh)2][ClO4]2 ((R)-3) and [Fe((R)-LPh)((S)-LPh)][ClO4]2 ((RS)-3; LPh=2,6-bis{4-phenyloxazolinyl}pyridine); and [Fe((R)-LiPr)2][ClO4]2 ((R)-4) and [Fe((R)-LiPr)((S)-LiPr)][ClO4]2 ((RS)-4; LiPr=2,6-bis{4-isopropyloxazolinyl}pyridine). Solid (R)-3⋅MeNO2 exhibits an unusual very gradual, but discontinuous thermal spin-crossover with an approximate Tmath formula of 350 K. The discontinuity around 240 K lies well below Tmath formula , and is unconnected to a crystallographic phase change occurring at 170 K. Rather, it can be correlated with a gradual ordering of the ligand conformation as the temperature is raised. The other solid compounds either exhibit spin-crossover above room temperature (1 and (RS)-3), or remain high-spin between 5–300 K [(R)-2, (R)-4 and (RS)-4]. Homochiral (R)-3 and (R)-4 exhibit more twisted ligand conformations and coordination geometries than their heterochiral isomers, which can be attributed to steric clashes between ligand substituents [(R)-3]; or, between the isopropyl substituents of one ligand and the backbone of the other ((R)-4). In solution, (RS)-3 retains its structural integrity but (RS)-4 undergoes significant racemization through ligand redistribution by 1H NMR. (R)-4 and (RS)-4 remain high-spin in solution, whereas the other compounds all undergo spin-crossover equilibria. Importantly, Tmath formula for (R)-3 (244 K) is 34 K lower than for (RS)-3 (278 K) in CD3CN, which is the first demonstration of chiral discrimination between metal ion spin states in a molecular complex

The Speciation of Homochiral and Heterochiral Diastereomers of Homoleptic Cobalt(II) and Zinc(II) PyBox Complexes

Homochiral [M((R)-LR)2]2+ and heterochiral [M((R)-LR)((S)-LR)]2+ isomers of [Zn(LPh)2][BF4]2, [Zn(LiPr)2][BF4]2, [Co(LPh)2][BF4]2, and [Co(LiPr)2][BF4]2 (LPh = 2,6-bis(4-phenyloxazolinyl)pyridine; LiPr = 2,6-bis(4-isopropyloxazolinyl)pyridine) have been prepared and characterised. Six of the eight compounds were crystallographically characterised, showing that steric repulsions between ligand substituents lead to more distorted coordination geometries in the homochiral isomers, especially in the LiPr complexes. Heterochiral [M((R)-LiPr)((S)-LiPr)]2+ (M = Zn or Co) undergoes partial racemisation in CD3CN through ligand redistribution reactions, whereas [M((R)-LPh)((S)-LPh)]2+ does not (in agreement with previous reports). This may be a consequence of intramolecular π... π - interactions in [M((R)-LPh)((S)-LPh)]2+, whereby each pyridyl group is sandwiched between two phenyl substituents from the other LPh ligand. These π... π -interactions are disrupted in homochiral [M((R)-LR)2]2+, owing to the aforementioned steric clash between phenyl substituents in that isomer

Neutrino-driven Explosions

The question why and how core-collapse supernovae (SNe) explode is one of the central and most long-standing riddles of stellar astrophysics. A solution is crucial for deciphering the SN phenomenon, for predicting observable signals such as light curves and spectra, nucleosynthesis, neutrinos, and gravitational waves, for defining the role of SNe in the evolution of galaxies, and for explaining the birth conditions and properties of neutron stars (NSs) and stellar-mass black holes. Since the formation of such compact remnants releases over hundred times more energy in neutrinos than the SN in the explosion, neutrinos can be the decisive agents for powering the SN outburst. According to the standard paradigm of the neutrino-driven mechanism, the energy transfer by the intense neutrino flux to the medium behind the stagnating core-bounce shock, assisted by violent hydrodynamic mass motions (sometimes subsumed by the term "turbulence"), revives the outward shock motion and thus initiates the SN blast. Because of the weak coupling of neutrinos in the region of this energy deposition, detailed, multidimensional hydrodynamic models including neutrino transport and a wide variety of physics are needed to assess the viability of the mechanism. Owing to advanced numerical codes and increasing supercomputer power, considerable progress has been achieved in our understanding of the physical processes that have to act in concert for the success of neutrino-driven explosions. First studies begin to reveal observational implications and avenues to test the theoretical picture by data from individual SNe and SN remnants but also from population-integrated observables. While models will be further refined, a real breakthrough is expected through the next Galactic core-collapse SN, when neutrinos and gravitational waves can be used to probe the conditions deep inside the dying star. (abridged)Comment: Author version of chapter for 'Handbook of Supernovae,' edited by A. Alsabti and P. Murdin, Springer. 54 pages, 13 figure

Towards Logical Specification of Statistical Machine Learning

We introduce a logical approach to formalizing statistical properties of machine learning. Specifically, we propose a formal model for statistical classification based on a Kripke model, and formalize various notions of classification performance, robustness, and fairness of classifiers by using epistemic logic. Then we show some relationships among properties of classifiers and those between classification performance and robustness, which suggests robustness-related properties that have not been formalized in the literature as far as we know. To formalize fairness properties, we define a notion of counterfactual knowledge and show techniques to formalize conditional indistinguishability by using counterfactual epistemic operators. As far as we know, this is the first work that uses logical formulas to express statistical properties of machine learning, and that provides epistemic (resp. counterfactually epistemic) views on robustness (resp. fairness) of classifiers.Comment: SEFM'19 conference paper (full version with errors corrected

Neutron Stars in Teleparallel Gravity

In this paper we deal with neutron stars, which are described by a perfect fluid model, in the context of the teleparallel equivalent of general relativity. We use numerical simulations to find the relationship between the angular momentum of the field and the angular momentum of the source. Such a relation was established for each stable star reached by the numerical simulation once the code is fed with an equation of state, the central energy density and the ratio between polar and equatorial radii. We also find a regime where linear relation between gravitational angular momentum and moment of inertia (as well as angular velocity of the fluid) is valid. We give the spatial distribution of the gravitational energy and show that it has a linear dependence with the squared angular velocity of the source.Comment: 19 pages, 14 figures. arXiv admin note: text overlap with arXiv:1206.331

Gravitational Waves from Gravitational Collapse

Gravitational wave emission from the gravitational collapse of massive stars has been studied for more than three decades. Current state of the art numerical investigations of collapse include those that use progenitors with realistic angular momentum profiles, properly treat microphysics issues, account for general relativity, and examine non--axisymmetric effects in three dimensions. Such simulations predict that gravitational waves from various phenomena associated with gravitational collapse could be detectable with advanced ground--based and future space--based interferometric observatories.Comment: 68 pages including 13 figures; revised version accepted for publication in Living Reviews in Relativity (http://www.livingreviews.org

Evaluation of infectivity and transmission of different Asian foot-and-mouth disease viruses in swine

Most isolates of foot-and-mouth disease virus (FMDV) display a broad host range. Since the late 1990s, the genetic lineage of PanAsia topotype FMDV serotype O has caused epidemics in the Far East, Africa, the United Kingdom, France, the Netherlands, and numerous other countries throughout Europe and Asia. In contrast, there are several FMDV isolates that exhibit a more restricted host range. A Cathay topotype isolate of FMDV serotype O from the 1997 epizootic in Taiwan (O/TAW/97) demonstrated restricted host specificity, only infecting swine. Methods used to evaluate infectivity and pathogenicity of FMDV isolates in cattle are well-documented, but there has been less progress studying transmission and pathogenicity of FMDV isolates in pigs. In previous studies designed to examine pathogenicity, various chimeric viruses derived from O/TAW/97 were intradermally inoculated in the heel bulb of pigs. Subsequent quantitative scoring of disease and evaluation of virus released into nasal secretions and blood was assessed. Here we prove the usefulness of this method in direct and contact inoculated pigs to evaluate infectivity, pathogenicity and transmission of different Asian FMDV isolates. Virus strains within the Cathay topotype were highly virulent in swine producing a synchronous disease in inoculated animals and were efficiently spread to in-contact naive pigs, while virus strains from the PanAsia topotype displayed more heterogeneous properties