Theoretical study of two states reactivity of methane activation on iron atom and iron dimer

Density functional theory (DFT) calculations have been carried out to explore the catalytic activation of C–H bonds in methane by the iron atom, Fe, and the iron dimer, Fe2. For methane activation on an Fe atom, the calculations suggest that the activation of the first C–H bond is mediated via the triplet excited-state potential energy surface (PES), with initial excitation of Fe to the triplet state being necessary for the reaction to be energetically feasible. Compared with the breaking of the first C–H bond, the cleavage of the second C–H bond is predicted to involve a significantly higher barrier, which could explain experimental observations of the HFeCH3 complex rather than CH2FeH2 in the activation of methane by an Fe atom. For methane activation on an iron dimer, the cleavage of the first C–H bond is quite facile with a barrier only 11.2, 15.8 and 8.4 kcal/mol on the septet state energy surface at the B3LYP/6-311+G(2df,2dp), BPW91/6-311+G(2df,2dp) and M06/B3LYP level, respectively. Cleavage of the second C–H bond from HFe2CH3 involves a barrier calculated respectively as 18.0, 10.7 and 12.4 kcal/mol at the three levels. The results suggest that the elimination of hydrogen from the dihydrogen complex is a rate-determining step. Overall, our results indicate that the iron dimer Fe2 has a stronger catalytic effect on the activation of methane than the iron atom.

Adatom CCV Auger rates via the local density of states

In this letter the core-core-valence Auger transitions of an atomic impurity, both in bulk or adsorbed on a jellium-like surface, are computed within a DFT framework. The Auger rates calculated by the Fermi golden rule are compared with those determined by an approximate and simpler expression. This is based on the local density of states (LDOS) with a core hole present, in a region around the impurity nucleus. Different atoms, Na and Mg, solids, Al and Ag, and several impurity locations are considered. We obtain an excellent agreement between KL1V and KL23V rates worked out with the two approaches. The radius of the sphere in which we calculate the LDOS is the relevant parameter of the simpler approach. Its value only depends on the atomic species regardless of the location of the impurity and the type of substrate. (C) 2003 Elsevier B.V. All rights reserved.

An approach for identifying the limit states of resilience of a water supply system

This paper presents an approach for identifying the limit states of resilience in a water supply system when influenced by different types of pressure (disturbing) forces. Understanding of systemic resilience facilitates identification of the trigger points for early managerial action to avoid further loss of ability to provide satisfactory service availability when the ability to supply water is under pressure. The approach proposed here is to illustrate the usefulness of a surrogate measure of resilience depicted in a three dimensional space encompassing independent pressure factors. That enables visualisation of the transition of the system-state (resilience) between high to low resilience regions and acts as an early warning trigger for decision-making. The necessity of a surrogate measure arises as a means of linking resilience to the identified pressures as resilience cannot be measured directly. The basis for identifying the resilience surrogate and exploring the interconnected relationships within the complete system, is derived from a meta-system model consisting of three nested sub-systems representing the water catchment and reservoir; treatment plant; and the distribution system and end-users. This approach can be used as a framework for assessing levels of resilience in different infrastructure systems by identifying a surrogate measure and its relationship to relevant pressures acting on the system.

Ultimate flexural limit states analysis of prestressed concrete sleeper

Railway is one of the most important, reliable and widely used means of transportation, carrying freight, passengers, minerals, grains, etc. Thus, research on railway tracks is extremely important for the development of railway engineering and technologies. The safe operation of a railway track is based on the railway track structure that includes rails, fasteners, pads, sleepers, ballast, subballast and formation. Sleepers are very important components of the entire structure and may be made of timber, concrete, steel or synthetic materials. Concrete sleepers were first installed around the middle of last century and currently are installed in great numbers around the world. Consequently, the design of concrete sleepers has a direct impact on the safe operation of railways. The "permissible stress" method is currently most commonly used to design sleepers. However, the permissible stress principle does not consider the ultimate strength of materials, probabilities of actual loads, and the risks associated with failure, all of which could lead to the conclusion of cost-ineffectiveness and over design of current prestressed concrete sleepers. Recently the limit states design method, which appeared in the last century and has been already applied in the design of buildings, bridges, etc, is proposed as a better method for the design of prestressed concrete sleepers. The limit states design has significant advantages compared to the permissible stress design, such as the utilisation of the full strength of the member, and a rational analysis of the probabilities related to sleeper strength and applied loads. This research aims to apply the ultimate limit states design to the prestressed concrete sleeper, namely to obtain the load factors of both static and dynamic loads for the ultimate limit states design equations. However, the sleepers in rail tracks require different safety levels for different types of tracks, which mean the different types of tracks have different load factors of limit states design equations. Therefore, the core tasks of this research are to find the load factors of the static component and dynamic component of loads on track and the strength reduction factor of the sleeper bending strength for the ultimate limit states design equations for four main types of tracks, i.e., heavy haul, freight, medium speed passenger and high speed passenger tracks. To find those factors, the multiple samples of static loads, dynamic loads and their distributions are needed. In the four types of tracks, the heavy haul track has the measured data from Braeside Line (A heavy haul line in Central Queensland), and the distributions of both static and dynamic loads can be found from these data. The other three types of tracks have no measured data from sites and the experimental data are hardly available. In order to generate the data samples and obtain their distributions, the computer based simulations were employed and assumed the wheel-track impacts as induced by different sizes of wheel flats. A valid simulation package named DTrack was firstly employed to generate the dynamic loads for the freight and medium speed passenger tracks. However, DTrack is only valid for the tracks which carry low or medium speed vehicles. Therefore, a 3-D finite element (FE) model was then established for the wheel-track impact analysis of the high speed track. This FE model has been validated by comparing its simulation results with the DTrack simulation results, and with the results from traditional theoretical calculations based on the case of heavy haul track. Furthermore, the dynamic load data of the high speed track were obtained from the FE model and the distributions of both static and dynamic loads were extracted accordingly. All derived distributions of loads were fitted by appropriate functions. Through extrapolating those distributions, the important parameters of distributions for the static load induced sleeper bending moment and the extreme wheel-rail impact force induced sleeper dynamic bending moments and finally, the load factors, were obtained. Eventually, the load factors were obtained by the limit states design calibration based on reliability analyses with the derived distributions. After that, a sensitivity analysis was performed and the reliability of the achieved limit states design equations was confirmed. It has been found that the limit states design can be effectively applied to railway concrete sleepers. This research significantly contributes to railway engineering and the track safety area. It helps to decrease the failure and risks of track structure and accidents; better determines the load range for existing sleepers in track; better rates the strength of concrete sleepers to support bigger impact and loads on railway track; increases the reliability of the concrete sleepers and hugely saves investments on railway industries. Based on this research, many other bodies of research can be promoted in the future. Firstly, it has been found that the 3-D FE model is suitable for the study of track loadings and track structure vibrations. Secondly, the equations for serviceability and damageability limit states can be developed based on the concepts of limit states design equations of concrete sleepers obtained in this research, which are for the ultimate limit states.

Conceptual and thematic analysis of policies and guidelines on engineering asset management of different states in Australia

The role of government in developing policies and guidelines for asset management is becoming increasingly important especially in view of ageing infrastructure and increasing financial risks for building infrastructure. This paper reviews policies and guidelines developed by Australian state authorities against industry developed principles. It utilizes the software program Leximancer to; a) produce conceptual visualisations of the key themes and concepts embedded within state-wide policies and guidelines, and b) systematically compare the differing asset management foci between states. The analyses reveal mixed results in terms of policy priorities and guidelines for managing assets at a strategic level across states. This paper outlines a rigorous analytical methodology to inform specific policy changes.

Generation of active surface states of gold and the role of such states in electrocatalysis

The cyclic voltammetry behaviour of gold in aqueous media is often regarded in very simple terms as a combination of two distinct processes, double layer charging/discharging and monolayer oxide formation/removal. This view is questioned here on the basis of both the present results and earlier independent data by other authors. It was demonstrated in the present case that both severe cathodization or thermal pretreatment of polycrystalline gold in acid solution resulted in the appearance of substantial Faradaic responses in the double layer region. Such anamolous behaviour, as outlined recently also for other metals, is rationalized in terms of the presence of active metal atoms (which undergo premonolayer oxidation) at the electrode surface. Such behaviour, which is also assumed to correspond to that of active sites on conventional gold surfaces, is assumed to be of vital importance in electrocatalysis; in many instances the latter process is also quite marked in the double layer region.

High energy states of gold and their importance in electrocatalytic processes at surfaces and interfaces

The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

The role of defects, or active states, in surface electrochemistry with particular reference to gold in neutral solution

Metastable, active, or nonequilibrium states due to the presence of abnormal structures and various types of defects are well known in metallurgy. The role of such states at gold surfaces in neutral aqueous media (an important electrode system in the microsensor area) was explored using cyclic voltammetry. It was demonstrated that, as postulated in earlier work from this laboratory, there is a close relationship between premonolayer oxidation, multilayer hydrous oxide reduction and electrocatalytic behaviour in the case of this and other metal electrode systems. Some of the most active, and therefore most important, entities at surfaces (e.g., metal adatoms) are not readily imageable or detectable by high resolution surface microscopy techniques. Cyclic voltammetry, however, provides significant, though not highly specific, information about such species. The main conclusion is that further practical and theoretical work on active states of metal surfaces is highly desirable as their behaviour is not simple and is of major importance in many electrocatalytic processes.

Managing growth in the sunshine states : urbanization and planning in Queensland and Florida

This paper compares the urbanization and planning in the two sunshine states of Florida and Queensland highlighting the similarities and differences, evaluates how effective the growth management programs have been, and examines the recent changes and the challenges they bring to the respective states.

A higher education quality assurance model for small states : the Maldives case study

Increasing globalisation and local expansion of Higher Education presents challenges to manage quality of the education services. This study investigated key stakeholders' perspectives on what constitutes key elements and attributes of an effective Quality Assurance (QA) system in Higher Education. The findings highlighted the need for: i) legislation to support a strong QA regulatory framework, ii) independence of the QA agency, iii) development of minimum quality standards through broad stakeholder involvement, and iv) a cyclical approach. The findings of this study proposed a QA model which has implications for strengthening of HE QA systems of Small State.

The role of sleepiness, sleep disorders, and the work environment on heavy-vehicle crashes in 2 Australian states

Heavy-vehicle driving involves a challenging work environment and a high crash rate. We investigated the associations of sleepiness, sleep disorders, and work environment (including truck characteristics) with the risk of crashing between 2008 and 2011 in the Australian states of New South Wales and Western Australia. We conducted a case-control study of 530 heavy-vehicle drivers who had recently crashed and 517 heavy-vehicle drivers who had not. Drivers' crash histories, truck details, driving schedules, payment rates, sleep patterns, and measures of health were collected. Subjects wore a nasal flow monitor for 1 night to assess for obstructive sleep apnea. Driving schedules that included the period between midnight and 5:59 am were associated with increased likelihood of crashing (odds ratio = 3.42, 95% confidence interval: 2.04, 5.74), as were having an empty load (odds ratio = 2.61, 95% confidence interval: 1.72, 3.97) and being a less experienced driver (odds ratio = 3.25, 95% confidence interval: 2.37, 4.46). Not taking regular breaks and the lack of vehicle safety devices were also associated with increased crash risk. Despite the high prevalence of obstructive sleep apnea, it was not associated with the risk of a heavy-vehicle nonfatal, nonsevere crash. Scheduling of driving to avoid midnight-to-dawn driving and the use of more frequent rest breaks are likely to reduce the risk of heavy-vehicle nonfatal, nonsevere crashes by 2–3 times.

Bike share's impact on car use : evidence from the United States, Great Britain, and Australia

There are currently more than 400 cities operating bike share programs. Purported benefits of bike share programs include flexible mobility, physical activity, reduced congestion, emissions and fuel use. Implicit or explicit in the calculation of program benefits are assumptions regarding the modes of travel replaced by bike share journeys. This paper examines the degree to which car trips are replaced by bike share, through an examination of survey and trip data from bike share programs in Melbourne, Brisbane, Washing, D.C., London, and Minneapolis/St. Paul. A secondary and unique component of this analysis examines motor vehicle support services required for bike share fleet rebalancing and maintenance. These two components are then combined to estimate bike share’s overall contribution to changes in vehicle kilometres traveled. The results indicate that the estimated mean reduction in car use due to bike share is at least twice the distance covered by operator support vehicles, with the exception of London, in which the relationship is reversed, largely due to a low car mode substitution rate. As bike share programs mature, evaluation of their effectiveness in reducing car use may become increasingly important. This paper reveals that by increasing the convenience of bike share relative to car use and by improving perceptions of safety, the capacity of bike share programs to reduce vehicle trips and yield overall net benefits will be enhanced. Researchers can adapt the analytical approach proposed in this paper to assist in the evaluation of current and future bike share programs.

Thinking about internal states, a qualitative investigation into metacognitions in women with eating disorders

Background There is a need for qualitative research to help develop case conceptualisations to guide the development of Metacognitive Therapy interventions for Eating Disorders. Method A qualitative study informed by grounded theory methodology was conducted involving open-ended interviews with 27 women aged 18–55 years, who were seeking or receiving treatment for a diagnosed ED. Results The categories identified in this study appeared to be consistent with a metacognitive model including constructs of a Cognitive Attentional Syndrome and metacognitive beliefs. These categories appear to be transdiagnostic, and the interaction between the categories is proposed to explain the maintenance of EDs. Conclusions The transdiagnostic model proposed may be useful to guide the development of future metacognitive therapy interventions for EDs with the hope that this will lead to improved outcomes for individuals with EDs.

Air navigation services in Australia and the United States : a comparative case study

The central document governing the global organization of Air Navigation Services (ANS) is the Convention on International Civil Aviation, commonly referred to as the “Chicago Convention,” whose original version was signed in that city in 1944. In the Convention, Contracting States agreed to ensure the minimum standards of ANS established by ICAO, a specialized United Nations agency created by the Convention. Emanating from obligations under the Chicago Convention, ANS has traditionally provided by departments of national governments. However, there is a widespread trend toward transferring delivery of ANS services outside of line departments of national governments to independent agencies or corporations. The Civil Air Navigation Services Organisation (CANSO), which is the trade association for independent ANS providers, currently counts approximately 60 members, and is steadily growing. However, whatever delivery mechanisms are chosen, national governments remain ultimately responsible for ensuring that adequate ANS services are available. The provision by governments of ANS reflects the responsibility of the state for safety, international relations, and indirectly, the macroeconomic benefits of ensuring a sound infrastructure for aviation. ANS is a “public good” and an “essential good” provided to all aircraft using a country’s airfields and airspace. However, ANS also represents a service that directly benefits only a limited number of users, notably aircraft owners and operators. The idea that the users of the system, rather than the taxpaying public, should incur the costs associated with ANS provision is inherent in the commercialization process. However, ICAO sets out broad principles for the establishment of user charges, which member states are expected to comply with. ICAO states that only distance flown and aircraft weights are acceptable parameters for use in a charging system. These two factors are considered to be easy to measure, bear a reasonable relationship to the value of service received, and do not discriminate due to factors such as where the flight originated or the nation of aircraft registration.