General rules for predicting where a catalytic reaction should occur on metal surfaces: A density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces

To predict where a catalytic reaction should occur is a fundamental issue scientifically. Technologically, it is also important because it can facilitate the catalyst's design. However, to date, the understanding of this issue is rather limited. In this work, two types of reactions, CH4 CH3 + H and CO C + 0 on two transition metal surfaces, were chosen as model systems aiming to address in general where a catalytic reaction should occur. The dissociations of CH4 - CH3 + H and CO --> C + O and their reverse reactions on flat, stepped, and kinked Rh and Pd surfaces were studied in detail. We find the following: First, for the CH4 Ch(3) + H reaction, the dissociation barrier is reduced by similar to0.3 eV on steps and kinks as compared to that on flat surfaces. On the other hand, there is essentially no difference in barrier for the association reaction of CH3 + H on the flat surfaces and the defects. Second, for the CO C + 0 reaction, the dissociation barrier decreases dramatically (more than 0.8 eV on Rh and Pd) on steps and kinks as compared to that on flat surfaces. In contrast to the CH3 + H reaction, the C + 0 association reaction also preferentially occurs on steps and kinks. We also present a detailed analysis of the reaction barriers in which each barrier is decomposed quantitatively into a local electronic effect and a geometrical effect. Our DFT calculations show that surface defects such as steps and kinks can largely facilitate bond breaking, while whether the surface defects could promote bond formation depends on the individual reaction as well as the particular metal. The physical origin of these trends is identified and discussed. On the basis of our results, we arrive at some simple rules with respect to where a reaction should occur: (i) defects such as steps are always favored for dissociation reactions as compared to flat surfaces; and (ii) the reaction site of the association reactions is largely related to the magnitude of the bonding competition effect, which is determined by the reactant and metal valency. Reactions with high valency reactants are more likely to occur on defects (more structure-sensitive), as compared to reactions with low valency reactants. Moreover, the reactions on late transition metals are more likely to proceed on defects than those on the early transition metals.

How simple grazing rules can lead to persistent boundaries in vegetation communities.

Natural landscape boundaries between vegetation communities are dynamically influenced by the selective grazing of herbivores. Here we show how this may be an emergent property of very simple animal decisions, without the need for any sophisticated choice rules etc., using a model based on biased diffusion. Animal grazing intensity is coupled with plant competition, resulting in reaction-diffusion dynamics, from which stable boundaries spontaneously emerge. In the model, animals affect their resources by both consumption and trampling. It is assumed that forage consists of two heterogeneously distributed competing resource species, one that is preferred (grass) over the other (heather) by the animals. The solutions to the resulting system of differential equations for three cases a) optimal foraging, b) random walk foraging and c) taxis-diffusion are presented. Optimal and random foraging gave unrealistic results, but taxis-diffusion accorded well with field observations. Persistent boundaries between patches of near-monoculture vegetation were predicted, with these boundaries drifting in response to overall grazing pressure (grass advancing with increased grazing and vice versa). The reaction-taxis-diffusion model provides the first mathematical explanation for such vegetation mosaic dynamics and the parameters of the model are open to experimental testing.

Fusion rules for merging uncertain information

In previous papers, we have presented a logic-based framework based on fusion rules for merging structured news reports. Structured news reports are XML documents, where the textentries are restricted to individual words or simple phrases, such as names and domain-specific terminology, and numbers and units. We assume structured news reports do not require natural language processing. Fusion rules are a form of scripting language that define how structured news reports should be merged. The antecedent of a fusion rule is a call to investigate the information in the structured news reports and the background knowledge, and the consequent of a fusion rule is a formula specifying an action to be undertaken to form a merged report. It is expected that a set of fusion rules is defined for any given application. In this paper we extend the approach to handling probability values, degrees of beliefs, or necessity measures associated with textentries in the news reports. We present the formal definition for each of these types of uncertainty and explain how they can be handled using fusion rules. We also discuss the methods of detecting inconsistencies among sources.

Zipf and Type-Token rules for the English, Spanish, Irish and Latin languages

The Zipf curves of log of frequency against log of rank for a large English corpus of 500 million word tokens, 689,000 word types and for a large Spanish corpus of 16 million word tokens, 139,000 word types are shown to have the usual slope close to –1 for rank less than 5,000, but then for a higher rank they turn to give a slope close to –2. This is apparently mainly due to foreign words and place names. Other Zipf curves for highlyinflected Indo-European languages, Irish and ancient Latin, are also given. Because of the larger number of word types per lemma, they remain flatter than the English curve maintaining a slope of –1 until turning points of about ranks 30,000 for Irish and 10,000 for Latin. A formula which calculates the number of tokens given the number of types is derived in terms of the rank at the turning point, 5,000 for both English and Spanish, 30,000 for Irish and 10,000 for Latin.

Probing quantum communication rules by addition and subtraction of single photons to/from a light field

The possibility of arbitrarily "adding" and "subtracting" single photons to and from a light field may give access to a complete engineering of quantum states and to fundamental quantum phenomena. We experimentally implemented simple alternated sequences of photon creation and annihilation on a thermal field and used quantum tomography to verify the peculiar character of the resulting light states. In particular, as the final states depend on the order in which the two actions are performed, we directly observed the noncommutativity of the creation and annihilation operators, one of the cardinal concepts of quantum mechanics, at the basis of the quantum behavior of light. These results represent a step toward the full quantum control of a field and may provide new resources for quantum information protocols

Decision rules, energy metabolism and vigour of hermit-crab fights

Aggressive interactions between animals are often settled by the use of repeated signals that reduce the risk of injury from combat but are expected to be costly. The accumulation of lactic acid and the depletion of energy stores may constrain activity rates during and after fights and thus represent significant costs of signalling. We tested this by analysing the concentrations of lactate and glucose in the haemolymph of hermit crabs following agonistic interactions over the ownership of the gastropod shells that they inhabit. Attackers and defenders play distinct roles of sender and receiver that are fixed for the course of the encounter. Attackers perform bouts of 'shell rapping', which vary in vigour between attackers and during the course of the encounter, and are a key predictor of victory. In contrast to the agonistic behaviour of other species, we can quantify the vigour of fighting. We demonstrate, to our knowledge for the first time, an association between the vigour of aggressive activity and a proximate cost of signalling. We show that the lactate concentration in attackers increases with the amount of shell rapping, and that this appears to constrain the vigour of subsequent rapping. Furthermore, attackers, but not defenders, give up when the concentration of lactate is high. Glucose levels in attackers also increase with the amount of rapping they perform, but do not appear to influence their decision to give up. Defenders are more likely to lose when they have particularly low levels of glucose. We conclude that the two roles use different decision rules during these encounters.

Complete Sudoku - extra rules for more symmetry

We propose some extra rules to add to the well-known Sudoku puzzle and present an argument to justify their inclusion. The rules mean that puzzles can be created with fewer cells completed initially yet which still have only one solution. We have created a Web-based program which can be used to generate and solve both standard and extended (Complete) puzzles.

Cumulative or sequential assessment during hermit crab shell fights: effects of oxygen on decision rules

Agonistic interactions between animals are often settled by the use of repeated signals which advertise the resource-holding potential of the sender. According to the sequential assessment game this repetition increases the accuracy with which receivers may assess the signal, but under the cumulative assessment model the repeated performances accumulate to give a signal of stamina. These models may be distinguished by the temporal pattern of signalling they predict and by the decision rules used by the contestants. Hermit crabs engage in shell fights over possession of the gastropod shells that they inhabit. During these interactions the two roles of signaller and receiver may be examined separately because they are fixed for the duration of the encounter. Attackers rap their shell against that of the defender in a series of bouts whereas defenders remain tightly withdrawn into their shells for the duration of the contest. At the end of a fight the attacker may evict the defender from its shell or decide to give up without first effecting an eviction; the decision for defenders is either to maintain a grip on its shell or to release the shell and allow itself to be evicted. We manipulated fatigue levels separately for attackers and defenders, by varying the oxygen concentration of the water that they are held in prior to fighting, and examined the effects that this has on the likelihood of each decision and on the temporal pattern of rapping. We show that the vigour of rapping and the likelihood of eviction are reduced when the attacker is subjected to low oxygen but that this treatment has no effect on rates of eviction when applied to defenders. We conclude that defenders compare the vigour of rapping with an absolute threshold rather than with a relative threshold when making their decision. The data are compatible with the cumulative assessment model and with the idea that shell rapping signals the stamina of attackers, but do not fit the predictions of the sequential assessment game.