State-resolved gas-surface reactivity of methane in the symmetric C-H stretch vibration on Ni(100)

The state-resolved reactivity of CH4 in its totally symmetric C-H stretch vibration (�1) has been measured on a Ni(100) surface. Methane molecules were accelerated to kinetic energies of 49 and 63:5 kJ=mol in a molecular beam and vibrationally excited to �1 by stimulated Raman pumping before surface impact at normal incidence. The reactivity of the symmetric-stretch excited CH4 is about an order of magnitude higher than that of methane excited to the antisymmetric stretch (�3) reported by Juurlink et al. [Phys. Rev. Lett. 83, 868 (1999)] and is similar to that we have previously observed for the excitation of the first overtone (2�3). The difference between the state-resolved reactivity for �1 and �3 is consistent with predictions of a vibrationally adiabatic model of the methane reaction dynamics and indicates that statistical models cannot correctly describe the chemisorption of CH4 on nickel.

Mode-specificity and transition state-specific energy redistribution in the chemisorption of CH4 on Ni{100}

We have investigated methane (CH4) dissociative chemisorption on the Ni{100} surface by first-principles molecular dynamics (MD) simulations. Our results show that this reaction is mode-specific, with the n1 state being the most strongly coupled to efficient energy flow into the reaction coordinate when the molecule reaches the transition state. By performing MD simulations for two different transition state (TS) structures we provide evidence of TS structure-specific energy redistribution in methane chemisorption. Our results are compared with recently reported state-resolved measurement of methane adsorption probability on nickel surfaces, and we find that a strong correlation exists between the highest vibrational efficacy measured on Ni{100} for the n1 state and the calculated highest fractional vibrational energy content in this mode.

Structure and stability of two polymorphs of creatine and its monohydrate

An experimental search for crystalline forms of creatine including a variable temperature X-ray powder diffraction study has produced three polymorphs and a formic acid solvate. The crystal structures of creatine forms I and II were determined from X-ray powder diffraction data plus the creatine formic acid (1 : 1) solvate structure was obtained by single crystal X-ray diffraction methods. Evidence of a third polymorphic form of creatine obtained by rapid desolvation of creatine monohydrate is also presented. The results highlight the role of automated parallel crystallisation, slurry experiments and VT-XRPD as powerful techniques for effective physical form screening. They also highlight the importance of various complementary analytical techniques in structural characterisation and in achieving better understanding of the relationship between various solid-state forms. The structural relationships between various solid-state forms of creatine using the XPac method provided a rationale for the different relative stabilities of forms I and II of creatine with respect to the monohydrate form.

Phosphorescence quantum yield enhanced by intermolecular hydrogen bonds in Cu4I4 clusters in the solid state

Organo-copper(I) halide complexes with a Cu4I4 cubane core and cyclic amines as ligands have been synthesized and their crystal structures have been defined. Their solid state photophysical properties have been measured and correlated with the crystal structure and packing. A unique and remarkably high luminescence quantum yield (76%) has been measured for one of the complexes having the cubane clusters arranged in a columnar structure and held together by N–HI hydrogen bonds. This high luminescence quantum yield is correlated with a slow radiationless deactivation rate of the excited state and suggests a rather strong enhancement of the cubane core rigidity bestowed by the hydrogen bond pattern. Some preliminary thin film deposition experiments show that these compounds could be considered to be good candidates for applications in electroluminescent devices because of their bright luminescence, low cost and relatively easy synthesis processes

An evaluation of decadal probability forecasts from state-of-the-art climate models

While state-of-the-art models of Earth's climate system have improved tremendously over the last 20 years, nontrivial structural flaws still hinder their ability to forecast the decadal dynamics of the Earth system realistically. Contrasting the skill of these models not only with each other but also with empirical models can reveal the space and time scales on which simulation models exploit their physical basis effectively and quantify their ability to add information to operational forecasts. The skill of decadal probabilistic hindcasts for annual global-mean and regional-mean temperatures from the EU Ensemble-Based Predictions of Climate Changes and Their Impacts (ENSEMBLES) project is contrasted with several empirical models. Both the ENSEMBLES models and a “dynamic climatology” empirical model show probabilistic skill above that of a static climatology for global-mean temperature. The dynamic climatology model, however, often outperforms the ENSEMBLES models. The fact that empirical models display skill similar to that of today's state-of-the-art simulation models suggests that empirical forecasts can improve decadal forecasts for climate services, just as in weather, medium-range, and seasonal forecasting. It is suggested that the direct comparison of simulation models with empirical models becomes a regular component of large model forecast evaluations. Doing so would clarify the extent to which state-of-the-art simulation models provide information beyond that available from simpler empirical models and clarify current limitations in using simulation forecasting for decision support. Ultimately, the skill of simulation models based on physical principles is expected to surpass that of empirical models in a changing climate; their direct comparison provides information on progress toward that goal, which is not available in model–model intercomparisons.

Estimating Lorenz's reference state in an ocean with a nonlinear equation of state for seawater

The study of the mechanical energy budget of the oceans using Lorenz available potential energy (APE) theory is based on knowledge of the adiabatically re-arranged Lorenz reference state of minimum potential energy. The compressible and nonlinear character of the equation of state for seawater has been thought to cause the reference state to be ill-defined, casting doubt on the usefulness of APE theory for investigating ocean energetics under realistic conditions. Using a method based on the volume frequency distribution of parcels as a function of temperature and salinity in the context of the seawater Boussinesq approximation, which we illustrate using climatological data, we show that compressibility effects are in fact minor. The reference state can be regarded as a well defined one-dimensional function of depth, which forms a surface in temperature, salinity and density space between the surface and the bottom of the ocean. For a very small proportion of water masses, this surface can be multivalued and water parcels can have up to two statically stable levels in the reference density profile, of which the shallowest is energetically more accessible. Classifying parcels from the surface to the bottom gives a different reference density profile than classifying in the opposite direction. However, this difference is negligible. We show that the reference state obtained by standard sorting methods is equivalent, though computationally more expensive, to the volume frequency distribution approach. The approach we present can be applied systematically and in a computationally efficient manner to investigate the APE budget of the ocean circulation using models or climatological data.

The slowly evolving background state of the atmosphere

The theory of wave–mean flow interaction requires a partition of the atmospheric flow into a notional background state and perturbations to it. Here, a background state, known as the Modified Lagrangian Mean (MLM), is defined as the zonally symmetric state obtained by requiring that every potential vorticity (PV) contour lying within an isentropic layer encloses the same mass and circulation as in the full flow. For adiabatic and frictionless flow, these two integral properties are time-invariant and the MLM state is a steady solution of the primitive equations. The time dependence in the adiabatic flow is put into the perturbations, which can be described by a wave-activity conservation law that is exact even at large amplitude. Furthermore, the effects of non-conservative processes on wave activity can be calculated from the conservation law. A new method to calculate the MLM state is introduced, where the position of the lower boundary is obtained as part of the solution. The results are illustrated using Northern Hemisphere ERA-Interim data. The MLM state evolves slowly, implying that the net non-conservative effects are weak. Although ‘adiabatic eddy fluxes’ cannot affect the MLM state, the effects of Rossby-wave breaking, PV filamentation and subsequent dissipation result in sharpening of the polar vortex edge and meridional shifts in the MLM zonal flow, both at tropopause level and on the winter stratospheric vortex. The rate of downward migration of wave activity during stratospheric sudden warmings is shown to be given by the vertical scale associated with polar vortex tilt divided by the time-scale for wave dissipation estimated from the wave-activity conservation law. Aspects of troposphere–stratosphere interaction are discussed. The new framework is suitable to examine the climate and its interactions with disturbances, such as midlatitude storm tracks, and makes a clean partition between adiabatic and non-conservative processes.

Do laws influence the cost of real estate brokerage services? A state fixed effects approach

A FTC-DOJ study argues that state laws and regulations may inhibit the unbundling of real estate brokerage services in response to new technology. Our data show that 18 states have changed laws in ways that promote unbundling since 2000. We model brokerage costs as measured by number of agents in a state-level annual panel vector autoregressive framework, a novel way of analyzing wasteful competition. Our findings support a positive relationship between brokerage costs and lagged house price and transactions. We find that change in full-service brokers responds negatively (by well over two percentage points per year) to legal changes facilitating unbundling

Examining the relationships between Holocene climate change, hydrology, and human society in Ireland

This thesis explores human-environment interactions during the Mid-Late Holocene in raised bogs in central Ireland. The raised bogs of central Ireland are widely-recognised for their considerable palaeoenvironmental and archaeological resources: research over the past few decades has established the potential for such sites to preserve sensitive records of Holocene climatic variability expressed as changes in bog surface wetness (BSW); meanwhile archaeological investigations over the past century have uncovered hundreds of peatland archaeological features dating from the Neolithic through to the Post-Medieval period including wooden trackways, platforms, and deposits of high-status metalwork. Previous studies have attempted to explore the relationship between records of past environmental change and the occurrence of peatland archaeological sites reaching varying conclusions. More recently, environmentally-deterministic models of human-environment interaction in Irish raised bogs at the regional scale have been explicitly tested leading to the conclusion that there is no relationship between BSW and past human activity. These relationships are examined in more detail on a site-by-site basis in this thesis. To that end, testate amoebae-derived BSW records from nine milled former raised bogs in central Ireland were produced from sites with known and dated archaeological records. Relationships between BSW records and environmental conditions within the study area were explored through both the development of a new central Ireland testate amoebae transfer function and through comparisons between recent BSW records and instrumental weather data. Compilation of BSW records from the nine fossil study sites show evidence both for climate forcing, particularly during 3200-2400 cal BP, as well as considerable inter-site variability. Considerable inter-site variability was also evident in the archaeological records of the same sites. Whilst comparisons between BSW and archaeological records do not show a consistent linear relationship, examination of records on a site-by-site basis were shown to reveal interpretatively important contingent relationships. It is concluded therefore, that future research on human-environment interactions should focus on individual sites and should utilise theoretical approaches from the humanities in order to avoid the twin pitfalls of masking important local patterns of change, and of environmental determinism.

Processes controlling surface, bottom and lateral melt of Arctic sea ice in a state of the art sea ice model

We present a modelling study of processes controlling the summer melt of the Arctic sea ice cover. We perform a sensitivity study and focus our interest on the thermodynamics at the ice–atmosphere and ice–ocean interfaces. We use the Los Alamos community sea ice model CICE, and additionally implement and test three new parametrization schemes: (i) a prognostic mixed layer; (ii) a three equation boundary condition for the salt and heat flux at the ice–ocean interface; and (iii) a new lateral melt parametrization. Recent additions to the CICE model are also tested, including explicit melt ponds, a form drag parametrization and a halodynamic brine drainage scheme. The various sea ice parametrizations tested in this sensitivity study introduce a wide spread in the simulated sea ice characteristics. For each simulation, the total melt is decomposed into its surface, bottom and lateral melt components to assess the processes driving melt and how this varies regionally and temporally. Because this study quantifies the relative importance of several processes in driving the summer melt of sea ice, this work can serve as a guide for future research priorities.

State ownership, bank loans, and corporate investment

We study the effect of bank loans on Chinese publicly listed firms' investment decisions based on the underinvestment and overinvestment theories of leverage. Evidence from China is of particular importance because China is the world's largest emerging and transitional economy. At first we show that there is a negative relationship between bank loan ratios and investment for Chinese publicly listed firms. And this negative relationship is much stronger for firms with low growth than firms with high growth. Secondly, we find that both short-term and long-term loan ratios are negatively correlated with investment. However, the higher the long-term loan ratios are, the weaker the negative relationship between long-term loan ratios and investment is. Thirdly, firm ownership only matters to the effect of short-term bank loans on investment in our sample. That is, the negative relationship between short-term loan ratios and investment is weaker for SOEs than for non-SOEs. Lastly, we show that the reform of China's banking system in 2003 has not strengthened the negative relationship between bank loans and investment. Our findings suggest that although Chinese state-owned banks are severely intervened by government policies, they still have a disciplining role on firms' investment, especially in firms with low growth.

It’s not the size, it’s the relationship: from ‘small states’ to asymmetry

Debate about the definition of “small state” has produced more fragmentation than consensus, even as the literature has demonstrated its subjects’ roles in joining international organizations propagating norms, executing creative diplomacy, influencing allies, avoiding and joining conflicts, and building peace. However, work on small states has struggled to identify commonalities in these states’ international relations, to cumulate knowledge, or to impact broader IR theory. This paper advocates a changed conceptual and definitional framework. Analysis of “small states” should pivot to examine the dynamics of the asymmetrical relationships in which these states are engaged. Instead of seeking an overall metric for size as the relevant variable—falling victim in a different way Dahl’s “lump-of-power fallacy,” we can recognize the multifaceted, variegated nature of power, whether in war or peacetime.