Emulation of chiral hydrogenation catalysts by adsorbtion of small molecules onto Ni surfaces

Adsorption of small molecules on the Ni{111} and NiO{111} surfaces is investigated under UHV and elevated pressures (~10-1 mbar) of hydrogen and water. The molecules considered are chosen for their relevance to understanding the mechanism of enantioselective hydrogenation on Raney Nickel modified by chiral molecules. Adsorption of water onto, and its subsequent reaction with, oxygen-covered Ni{111} is dependent on the initial atomic oxygen coverage. An OH species (O1s binding energy 531.5eV), oriented perpendicular to the surface, forms at atomic oxygen coverages <0.25ML. The reaction does not consume all the adsorbed oxygen for coverages ≥0.12ML. The p(2×2) atomic oxygen uperstructure is unreactive, while an OH species is formed on the p(√3×√3) superstructure at binding energy 530.9eV. L-alanine is adsorbed on Ni{111} as a model chiral modifier molecule. At low coverages, alanine forms a presumed tridentate alaninate species for coverages ≥0.11ML at 250K. A minority, bidentate zwitterionic species forms at coverages >0.11ML, but was not observed at 300K. Saturation occurs at 0.25ML. At high alanine coverages (≥0.19ML) and H2 pressure (≥1×10-2 mbar), the tridentate L-alaninate converts to bidentate zwitterionic L-alanine at 300K. Thermal evolution of L-alanine on Ni{111} under varying hydrogen pressures is examined. Adsorption of L-alanine onto hydroxylated NiO{111} at 300K in UHV, mimicking a catalyst surface under aqueous conditions, yields the tridentate alaninate which is immune to the effects of elevated hydrogen pressure. Exposing the L-alanine/Ni{111} adsorption system to water (≤10-1 mbar) oxidises the surface and recreates the L-alanine/hydroxylated NiO{111} system. Pyruvic acid on Ni{111} is examined as a model for hydrogenation substrate adsorption. Behaviour is coverage dependent and several conformations are possible at low coverages (≤0.1ML). Annealing at coverages <0.2ML causes a condensation reaction, releasing water onto the surface. High coverages do not condense and a saturation coverage of ~0.35ML is found.

Emulating AOGCM results using simple climate models

Three simple climate models (SCMs) are calibrated using simulations from atmosphere ocean general circulation models (AOGCMs). In addition to using two conventional SCMs, results from a third simpler model developed specifically for this study are obtained. An easy to implement and comprehensive iterative procedure is applied that optimises the SCM emulation of global-mean surface temperature and total ocean heat content, and, if available in the SCM, of surface temperature over land, over the ocean and in both hemispheres, and of the global-mean ocean temperature profile. The method gives best-fit estimates as well as uncertainty intervals for the different SCM parameters. For the calibration, AOGCM simulations with two different types of forcing scenarios are used: pulse forcing simulations performed with 2 AOGCMs and gradually changing forcing simulations from 15 AOGCMs obtained within the framework of the Fourth Assessment Report of the Intergovernmental Panel on Climate Change. The method is found to work well. For all possible combinations of SCMs and AOGCMs the emulation of AOGCM results could be improved. The obtained SCM parameters depend both on the AOGCM data and the type of forcing scenario. SCMs with a poor representation of the atmosphere thermal inertia are better able to emulate AOGCM results from gradually changing forcing than from pulse forcing simulations. Correct simultaneous emulation of both atmospheric temperatures and the ocean temperature profile by the SCMs strongly depends on the representation of the temperature gradient between the atmosphere and the mixed layer. Introducing climate sensitivities that are dependent on the forcing mechanism in the SCMs allows the emulation of AOGCM responses to carbon dioxide and solar insolation forcings equally well. Also, some SCM parameters are found to be very insensitive to the fitting, and the reduction of their uncertainty through the fitting procedure is only marginal, while other parameters change considerably. The very simple SCM is found to reproduce the AOGCM results as well as the other two comparably more sophisticated SCMs.

Turing, Kasparov and the future

The 'Turing 100' Conference in Manchester was the main event of the Turing Centenary Year in 2012. This is a report and reflection on Kasparov's popular talk. Within it, he explained how Turing and influenced computer chess, his career and the chess community. Kasparov also played Chessbase's 'TURING' emulation of Turing's second paper chess engine, here labelled 'AT2'. Quasi Turing-tests, computer contributions to world championship chess, and suspected cheating in chess are also mentioned.