First-principles, atomistic thermodynamics for oxidation catalysis

Present knowledge of the function of materials is largely based on studies (experimental and theoretical) that are performed at low temperatures and ultra-low pressures. However, the majority of everyday applications, like e.g. catalysis, operate at atmospheric pressures and temperatures at or higher than 300 K. Here we employ ab initio, atomistic thermodynamics to construct a phase diagram of surface structures in the (T,p)-space from ultra-high vacuum to technically-relevant pressures and temperatures. We emphasize the value of such phase diagrams as well as the importance of the reaction kinetics that may be crucial e.g. close to phase boundaries.Comment: 4 pages including 2 figure files. Submitted to Phys. Rev. Lett. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

Morphological and statistical features of reaction zones in MILD and premixed combustion

Direct numerical simulation (DNS) results of turbulent MILD premixed and conventional (undiluted) premixed combustion have been investigated to shed light on the physical aspects of reaction zones and their morphology inMILD combustion. Results of a premixed case are used for comparative analyses. The analyses show that the regions with strong chemical activity in MILD combustion are distributed over a substantial portion of the computational domain unlike in the premixed case where these regions are confined to a small portion of the domain. Also, interactions of reaction zones are observed in MILD combustion with their spatial extent increasing with dilution level. These interactions give an appearance of distributed combustion for MILD conditions. The morphology of these reaction zones is investigated using the Minkowski functionals and shapefinders commonly employed in cosmology. Predominant sheet-like structures are observed for the premixed combustion case whereas a pancake-like structure is observed as the most probable shape for the MILD cases. Spatial and statistical analyses of various fluxes involved in a progress variable transport equation are conducted to study autoignitive or propagative characteristics of MILD reaction zones. The results suggest that there are local regions with autoignition, propagating-flames, and their coexistence for the conditions considered in this study. Typically, reaction dominated or ignition front and propagating-flame dominated regions are entangled for high dilution cases. Scalar gradient plays a strong role on whether reaction or propagating-flame dominated activities are favoured locally.YM acknowledges the financial support of Nippon Keidanren and Cambridge Overseas Trust. EPSRC support is acknowledged by NS. This work made use of the facilities of HECToR, the UK’s national high-performance computing service, which is provided by UoE HPCx Ltd at the University of Edinburgh, Cray Inc and NAG Ltd, and funded by the Office of Science and Technology through EPSRCs High End Computing Programme.This is the accepted manuscript. The final version is available from Elsevier at http://www.sciencedirect.com/science/article/pii/S001021801400128X

Switching the stereochemical outcome of 6-endo-trig cyclizations; Synthesis of 2,6-Cis-6-substituted 4-oxopipecolic acids

A base-mediated 6-endo-trig cyclization of readily accessible enone-derived α-amino acids has been developed for the direct synthesis of novel 2,6-cis-6- substituted-4-oxo-L-pipecolic acids. A range of aliphatic and aryl side chains were tolerated by this mild procedure to give the target compounds in good overall yields. Molecular modeling of the 6-endo-trig cyclization allowed some insight as to how these compounds were formed, with the enolate intermediate generated via an equilibrium process, followed by irreversible tautomerization/neutralization providing the driving force for product formation. Stereoselective reduction and deprotection of the resulting 2,6-cis-6-substituted 4-oxo-L-pipecolic acids to the corresponding 4-hydroxy-L-pipecolic acids was also performed

Shared neural representations of tactile roughness intensities by somatosensation and touch observation using an associative learning method

Previous human fMRI studies have reported activation of somatosensory areas not only during actual touch, but also during touch observation. However, it has remained unclear how the brain encodes visually evoked tactile intensities. Using an associative learning method, we investigated neural representations of roughness intensities evoked by (a) tactile explorations and (b) visual observation of tactile explorations. Moreover, we explored (c) modality-independent neural representations of roughness intensities using a cross-modal classification method. Case (a) showed significant decoding performance in the anterior cingulate cortex (ACC) and the supramarginal gyrus (SMG), while in the case (b), the bilateral posterior parietal cortices, the inferior occipital gyrus, and the primary motor cortex were identified. Case (c) observed shared neural activity patterns in the bilateral insula, the SMG, and the ACC. Interestingly, the insular cortices were identified only from the cross-modal classification, suggesting their potential role in modality-independent tactile processing. We further examined correlations of confusion patterns between behavioral and neural similarity matrices for each region. Significant correlations were found solely in the SMG, reflecting a close relationship between neural activities of SMG and roughness intensity perception. The present findings may deepen our understanding of the brain mechanisms underlying intensity perception of tactile roughness

Intersectional identities and dilemmas in interactions with health care professionals: An interpretative phenomenological analysis of British gay Muslim men

Individual interviews were conducted with six self-identified Muslim gay men living in London focusing on their experience of health service use. Transcripts were analysed using Interpretative Phenomenological Analysis. Analysis identified two major themes: namely, the close(d) community and self-management with health care professionals, detailing participants’ concerns regarding the risks of disclosing sexuality; and the authentic identity: “you’re either a Muslim or you’re gay, you can’t be both”, which delineated notions of incommensurate identity. Analysis highlights the need for health practitioners to have insight into the complexity of intersectional identities, identity disclosure dynamics, and the negative = consequences of assumptions made, be these heteronormative or faith-related

Composition, structure and stability of RuO_2(110) as a function of oxygen pressure

Using density-functional theory (DFT) we calculate the Gibbs free energy to determine the lowest-energy structure of a RuO_2(110) surface in thermodynamic equilibrium with an oxygen-rich environment. The traditionally assumed stoichiometric termination is only found to be favorable at low oxygen chemical potentials, i.e. low pressures and/or high temperatures. At realistic O pressure, the surface is predicted to contain additional terminal O atoms. Although this O excess defines a so-called polar surface, we show that the prevalent ionic model, that dismisses such terminations on electrostatic grounds, is of little validity for RuO_2(110). Together with analogous results obtained previously at the (0001) surface of corundum-structured oxides, these findings on (110) rutile indicate that the stability of non-stoichiometric terminations is a more general phenomenon on transition metal oxide surfaces.Comment: 12 pages including 5 figures. Submitted to Phys. Rev. B. Related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm

The interactions of winds from massive young stellar objects: X-ray emission, dynamics, and cavity evolution

2D axis-symmetric hydrodynamical simulations are presented which explore the interaction of stellar and disk winds with surrounding infalling cloud material. The star, and its accompanying disk, blow winds inside a cavity cleared out by an earlier jet. The collision of the winds with their surroundings generates shock heated plasma which reaches temperatures up to ~10^8 K. Attenuated X-ray spectra are calculated from solving the equation of radiative transfer along lines-of-sight. This process is repeated at various epochs throughout the simulations to examine the evolution of the intrinsic and attenuated flux. We find that the dynamic nature of the wind-cavity interaction fuels intrinsic variability in the observed emission on timescales of several hundred years. This is principally due to variations in the position of the reverse shock which is influenced by changes in the shape of the cavity wall. The collision of the winds with the cavity wall can cause clumps of cloud material to be stripped away. Mixing of these clumps into the winds mass-loads the flow and enhances the X-ray emission measure. The position and shape of the reverse shock plays a key role in determining the strength and hardness of the X-ray emission. In some models the reverse shock is oblique to much of the stellar and disk outflows, whereas in others it is closely normal over a wide range of polar angles. For reasonable stellar and disk wind parameters the integrated count rate and spatial extent of the intensity peak for X-ray emission agree with \textit{Chandra} observations of the deeply embedded MYSOs S106 IRS4, Mon R2 IRS3 A, and AFGL 2591.(abridged)Comment: 19 pages, 14 figures, accepted for publication in MNRA

On the validity of Damköhler's first hypothesis in turbulent Bunsen burner flames: A computational analysis

The validity of Damköhler's first hypothesis, which relates the turbulent flame speed to turbulent flame surface area under the condition where the integral length scale of turbulence is greater than the flame thickness, has been assessed using three-dimensional Direct Numerical Simulations (DNS) of turbulent premixed Bunsen burner flames over a range of values of Reynolds number, pressure and turbulence intensity. It has been found for the Bunsen configuration that the proportionality between volume-integrated burning rate and the overall flame surface area is not strictly maintained according to Damköhler's first hypothesis. The discrepancy is found to originate physically from the local stretch rate dependence of displacement speed, and this helps to explain differences observed previously between flames with and without mean curvature. Approximating the local density-weighted flame propagation speed with the unstrained laminar burning velocity is shown to be inaccurate, and can have a significant influence on the prediction of the overall burning rate for flames with non-zero mean curvature. Using a two-dimensional projection of the actual scalar gradient for flame area evaluation is shown to exacerbate the loss of proportionality between volume-integrated burning rate and the overall flame surface area. The current analysis identifies the conditions under which Damköhler's hypothesis remains valid and the necessary correction for non-zero mean flame curvature. Further, it has been demonstrated that surface-weighted stretch effects on displacement speed need to be accounted for in order to ensure the validity of Damköhler's hypothesis under all circumstances. Finally, it has been found that the volume-integrated density-weighted scalar dissipation rate remains proportional to the overall burning rate for all flames considered here irrespective of the value of Reynolds number, pressure and turbulence intensity. However, this proportionality is lost when the scalar dissipation rate is evaluated using the two-dimensional projection of the actual scalar gradient