Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Mn ion dissolution from MnS:a density functional theory study

The dissolution of MnS inclusions could induce pitting corrosion in stainless steels, but its dissolution mechanism is poorly understood at the atomic scale. With the help of ab initio molecular dynamics calculations, one inevitable step in the dissolution of MnS is studied by simulating the process of one Mn ion leaving the surface. The reaction mechanism is determined to contain three steps with two large barriers and a small one, leading to two slow steps in the Mn ion dissolution. Comparing to the Na ion dissolution from NaCl, the barriers of the Mn ion dissolution are much larger, which is a reflection of their different electronic structures.

Density Functional Theory Studies of Ethanol Decomposition on Rh(211)

Density functional theory calculations were carried out to examine the mechanism of ethanol decomposition on the Rh(211) surface. We found that there are two possible decomposition pathways: (1) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(3)CO -> CH(3) + CO -> CH(2) + CO -> CH + CO -> C + CO and (2) CH(3)CH(2)OH -> CH(3)CHOH -> CH(3)COH -> CH(2)COH -> CHCOH -> CHCO -> CH + CO -> C + CO. Both pathways have a common intermediate of CH(3)COH, and the key step is the formation of CH(3)CHOH species. According to our calculations, the mechanism of ethanol decomposition on Rh(211) is totally different from that on Rh(111): the reaction proceeds via CH(3)COH rather than an oxametallacycle species (-CH(2)CH(2)O- for Rh( 111)), which implies that the decomposition process is structure sensitive. Further analyses on electronic structures revealed that the preference of the initial C(alpha)-H path is mainly due to the significant reduction of d-electron energy in the presence of the transition state (TS) complex, which may stabilize the TS-surface system. The present work first provides a clear picture for ethanol decomposition on stepped Rh(211), which is an important first step to completely understand the more complicated reactions, like ethanol steam reforming and electrooxidation.

Opening eyes to opera: the process of translation for blind and partially-sighted audiences

In today’s rapidly developing digital age and increasingly socially-aware society, the notion of media accessibility is evolving in response to shifting audience expectations. Performing arts and media, such as opera, are called upon to include all audiences, and related audiovisual translation methods are progressing in this direction. These comprise audio description and touch tours for the blind and partially-sighted, two relatively new translation modalities which are consumer-oriented and require an original research design for the analysis of the translation processes involved. This research design follows two fundamental principles: (1) audience reception studies should be an integral part of the investigation into the translation process; and (2) the translation process is regarded as a network. Therefore, this paper explores the unique translation processes of audio description and touch tours within the context of live opera from the perspective of actor-network theory and by providing an overview of a reception project. Through discussion of the methodology and findings, this paper addresses the question of the impact of audience reception on the translation process.

Opening Eyes to Opera: the process of translation for blind and partially-sighted audiences

In today’s rapidly developing digital age and increasingly socially-aware society, the notion of media accessibility is evolving in response to shifting audience expectations. Performing arts and media, such as opera, are called upon to include all audiences, and related audiovisual translation methods are progressing in this direction. These comprise audio description and touch tours for the blind and partially-sighted, two relatively new translation modalities which are consumer-oriented and require an original research design for the analysis of the translation processes involved. This research design follows two fundamental principles: (1) audience reception studies should be an integral part of the investigation into the translation process; and (2) the translation process is regarded as a network. Therefore, this chapter explores the unique translation processes of audio description and touch tours within the context of live opera from the perspective of actor-network theory and by providing an overview of a reception project. Through discussion of the methodology and findings, this chapter addresses the question of the impact of audience reception on the translation process.

Practicing peace: Psychological roots of transforming conflicts

The practice of sustainable peace is a process that must be initiated, nourished and revised. The
“social energies” of conflict transformation – truth, mercy, justice, peace – offer a useful model to describe the transformative power of this practice. These social energies can be conceptualized as a combination of norms or values, on the one hand, and actions directed toward social reconstruction, on the other. As such, the social energies of conflict transformation are both the guideposts and the engine in the journey of practicing sustainable peace. This article begins by
linking psychological constructs of narrative/voice, empathy/altruism, individual/collective guilt, and security/fear with the social energies, highlighting the interdependence of processes and shifting the focus away from pathology toward an emphasis on harmony. An empirical application of how the four social energies contribute to the mobilization, maintenance and adaptations in on-going peace processes in post-war Guatemala is then presented. By analyzing the interaction among diverse actors and goals in the decade and a half since the signing of the 1996 Peace Accords, current theory is extended in two ways: a) differentiation between elite and grassroots initiatives, and b) specification and evaluation the impact of various efforts on episodic and structural violence. We conclude that although national and local processes have
had limited success, more integrated practices of truth, mercy, justice and peace are necessary if Guatemala is to make sustainable peace a reality. The findings from this case study have policy and practical implications for other countries facing protracted, violent conflict.

Young people exiting homelessness: An exploration of process, meaning and definition

In the past decade in particular, research attention has shifted from an almost exclusive focus on routes or pathways into homelessness towards the investigation of exits from homelessness. As well as demonstrating the multiple paths possible for young people who become homeless, recent research, and longitudinal studies in particular, has contributed to a more nuanced understanding of the complexity of the homeless pathways of young people. Nonetheless, knowledge and understanding of the nature of homeless exits, and of the mechanisms that facilitate the transition out of homelessness, is far from complete. This paper explores the processes surrounding the exit routes taken by young people out of homelessness and the meanings attached by them to these housing transitions based on selected findings from an ongoing qualitative longitudinal study of homeless youth in Dublin, Ireland. More broadly, the paper considers the utility of distinguishing between the types of routes that young people take out of homelessness, with particular attention to the notions of ‘independent’ and ‘dependent’ exits. The paper aims to further the discussion and debate on the conceptualisation of homeless exits and also discusses a number of policy implications arising from the study's findings.

How Video Lecture Capture affects Student Engagement in a University Computer Programming Course: Attendance, Video Viewing Behaviours and Student Attitudes

Introduction
The use of video capture of lectures in Higher Education is not a recent occurrence with web based learning technologies including digital recording of live lectures becoming increasing commonly offered by universities throughout the world (Holliman and Scanlon, 2004). However in the past decade the increase in technical infrastructural provision including the availability of high speed broadband has increased the potential and use of videoed lecture capture. This had led to a variety of lecture capture formats including pod casting, live streaming or delayed broadcasting of whole or part of lectures.
Additionally in the past five years there has been a significant increase in the popularity of online learning, specifically via Massive Open Online Courses (MOOCs) (Vardi, 2014). One of the key aspects of MOOCs is the simulated recording of lecture like activities. There has been and continues to be much debate on the consequences of the popularity of MOOCs, especially in relation to its potential uses within established University programmes.
There have been a number of studies dedicated to the effects of videoing lectures.
The clustered areas of research in video lecture capture have the following main themes:
• Staff perceptions including attendance, performance of students and staff workload
• Reinforcement versus replacement of lectures
• Improved flexibility of learning
• Facilitating engaging and effective learning experiences
• Student usage, perception and satisfaction
• Facilitating students learning at their own pace
Most of the body of the research has concentrated on student and faculty perceptions, including academic achievement, student attendance and engagement (Johnston et al, 2012).
Generally the research has been positive in review of the benefits of lecture capture for both students and faculty. This perception coupled with technical infrastructure improvements and student demand may well mean that the use of video lecture capture will continue to increase in frequency in the next number of years in tertiary education. However there is a relatively limited amount of research in the effects of lecture capture specifically in the area of computer programming with Watkins 2007 being one of few studies . Video delivery of programming solutions is particularly useful for enabling a lecturer to illustrate the complex decision making processes and iterative nature of the actual code development process (Watkins et al 2007). As such research in this area would appear to be particularly appropriate to help inform debate and future decisions made by policy makers.
Research questions and objectives
The purpose of the research was to investigate how a series of lecture captures (in which the audio of lectures and video of on-screen projected content were recorded) impacted on the delivery and learning of a programme of study in an MSc Software Development course in Queen’s University, Belfast, Northern Ireland. The MSc is conversion programme, intended to take graduates from non-computing primary degrees and upskill them in this area. The research specifically targeted the Java programming module within the course. It also analyses and reports on the empirical data from attendances and various video viewing statistics. In addition, qualitative data was collected from staff and student feedback to help contextualise the quantitative results.
Methodology, Methods and Research Instruments Used
The study was conducted with a cohort of 85 post graduate students taking a compulsory module in Java programming in the first semester of a one year MSc in Software Development. A pre-course survey of students found that 58% preferred to have available videos of “key moments” of lectures rather than whole lectures. A large scale study carried out by Guo concluded that “shorter videos are much more engaging” (Guo 2013). Of concern was the potential for low audience retention for videos of whole lectures.
The lecturers recorded snippets of the lecture directly before or after the actual physical delivery of the lecture, in a quiet environment and then upload the video directly to a closed YouTube channel. These snippets generally concentrated on significant parts of the theory followed by theory related coding demonstration activities and were faithful in replication of the face to face lecture. Generally each lecture was supported by two to three videos of durations ranging from 20 – 30 minutes.
Attendance
The MSc programme has several attendance based modules of which Java Programming was one element. In order to assess the consequence on attendance for the Programming module a control was established. The control used was a Database module which is taken by the same students and runs in the same semester.
Access engagement
The videos were hosted on a closed YouTube channel made available only to the students in the class. The channel had enabled analytics which reported on the following areas for all and for each individual video; views (hits), audience retention, viewing devices / operating systems used and minutes watched.
Student attitudes
Three surveys were taken in regard to investigating student attitudes towards the videoing of lectures. The first was before the start of the programming module, then at the mid-point and subsequently after the programme was complete.
The questions in the first survey were targeted at eliciting student attitudes towards lecture capture before they had experienced it in the programme. The midpoint survey gathered data in relation to how the students were individually using the system up to that point. This included feedback on how many videos an individual had watched, viewing duration, primary reasons for watching and the result on attendance, in addition to probing for comments or suggestions. The final survey on course completion contained questions similar to the midpoint survey but in summative view of the whole video programme.
Conclusions and Outcomes
The study confirmed findings of other such investigations illustrating that there is little or no effect on attendance at lectures. The use of the videos appears to help promote continual learning but they are particularly accessed by students at assessment periods. Students respond positively to the ability to access lectures digitally, as a means of reinforcing learning experiences rather than replacing them. Feedback from students was overwhelmingly positive indicating that the videos benefited their learning. Also there are significant benefits to part recording of lectures rather than recording whole lectures. The behaviour viewing trends analytics suggest that despite the increase in the popularity of online learning via MOOCs and the promotion of video learning on mobile devices in fact in this study the vast majority of students accessed the online videos at home on laptops or desktops However, in part, this is likely due to the nature of the taught subject, that being programming.
The research involved prerecording the lecture in smaller timed units and then uploading for distribution to counteract existing quality issues with recording entire live lectures. However the advancement and consequential improvement in quality of in situ lecture capture equipment may well help negate the need to record elsewhere. The research has also highlighted an area of potentially very significant use for performance analysis and improvement that could have major implications for the quality of teaching. A study of the analytics of the viewings of the videos could well provide a quick response formative feedback mechanism for the lecturer. If a videoed lecture either recorded live or later is a true reflection of the face to face lecture an analysis of the viewing patterns for the video may well reveal trends that correspond with the live delivery.

Finite element modelling of FRP-to-concrete bond behaviour using the concrete damage plasticity theory combined with a plastic degradation model

The technique of externally bonding fibre reinforced polymer (FRP) composites has been becoming popular worldwide for retrofitting existing reinforced concrete (RC) structures. A major failure mode in such strengthened structures is the debonding of FRP from the concrete substrate. The bond behaviour between FRP and concrete thus plays a crucial role in these structures. The FRP-to-concrete bond behaviour has been extensively investigated experimentally, commonly using the pull-off test of FRP-to-concrete bonded joint. Comparatively, much less research has been concerned with the numerical simulation of this bond behaviour, chiefly due to difficulties in accurately modelling the complex behaviour of concrete. This paper proposes a robust finite element (FE) model for simulating the bond behaviour in the entire loading process in the pull-off test. A concrete damage plasticity model based on the plastic degradation theory is proposed to overcome the weakness of the elastic degradation theory which has been commonly adopted in previous studies. The model produces results in very close agreement with test data. © Tsinghua University Press, Beijing and Springer-Verlag Berlin Heidelberg 2011.

Review of the area planning process (b)

This paper offers a commentary on the area planning reports form primary schools published by each of the Education and Library Boards (ELB) in June 2014. The format of the reports are broadly similar for each ELB, although there are some differences amongst them. All provide an overview on the policy context for the area planning process, a statistical picture of the schools in the ELB and detail on the issues considered for sets of schools within the ELB.

Knowledge Transfer in Quadruple Helix Ecosystems: An Absorptive Capacity Perspective

Increased understanding of knowledge transfer (KT) from universities to the wider regional knowledge ecosystem offers opportunities for increased regional innovation and commercialisation. The aim of this article is to improve the understanding of the KT phenomena in an open innovation context where multiple diverse quadruple helix stakeholders are interacting. An absorptive capacity-based conceptual framework is proposed, using a priori constructs which portrays the multidimensional process of KT between universities and its constituent stakeholders in pursuit of open innovation and commercialisation. Given the lack of overarching theory in the field, an exploratory, inductive theory building methodology was adopted using semi-structured interviews, document analysis and longitudinal observation data over a three-year period. The findings identify five factors, namely human centric factors, organisational factors, knowledge characteristics, power relationships and network characteristics, which mediate both the ability of stakeholders to engage in KT and the effectiveness of knowledge acquisition, assimilation, transformation and exploitation. This research has implications for policy makers and practitioners by identifying the need to implement interventions to overcome the barriers to KT effectiveness between regional quadruple helix stakeholders within an open innovation ecosystem.

Realist Evaluation: a theory driven approach.

Realistic Evaluation assumes that all programmes implemented in practice have an underlying theory to explain how a particular intervention is meant to work. The purpose of realist evaluation is to test the theoretical propositions underpinning the implementation of a programme in order to understand how and why it works, or might not work, in certain circumstances. The first stage of the realist evaluation is to track and articulate the programme theories to determine the evidence on the ‘official conjecture’ (Pawson et al 2004 pg 16) of how the programme is suppose to work in practice. These official conjectures are then tested and refined by gathering empirical evidence to establish causal relationships between a programme and its outcome. Evaluation of the factors and interactions between factors, supporting or hindering the implementation of a programme in practice facilitate theory refinement. Theory refinement is viewed as an iterative and cyclical process undertaken to synthesise the empirical evidence and develop mid-range theories which can be generalised and applied to other programmes to improve implementation and sustainability. In this symposium an example of realist evaluation used to test and refine the theory underpinning the implementation of Early Warning Systems (EWS) is provided to clarify how this theory driven approach can be applied in practice.

Context-dependent Combination of Sensor Information in Dempster-Shafer Theory for BDI

There has been much interest in the belief–desire–intention (BDI) agent-based model for developing scalable intelligent systems, e.g. using the AgentSpeak framework. However, reasoning from sensor information in these large-scale systems remains a significant challenge. For example, agents may be faced with information from heterogeneous sources which is uncertain and incomplete, while the sources themselves may be unreliable or conflicting. In order to derive meaningful conclusions, it is important that such information be correctly modelled and combined. In this paper, we choose to model uncertain sensor information in Dempster–Shafer (DS) theory. Unfortunately, as in other uncertainty theories, simple combination strategies in DS theory are often too restrictive (losing valuable information) or too permissive (resulting in ignorance). For this reason, we investigate how a context-dependent strategy originally defined for possibility theory can be adapted to DS theory. In particular, we use the notion of largely partially maximal consistent subsets (LPMCSes) to characterise the context for when to use Dempster’s original rule of combination and for when to resort to an alternative. To guide this process, we identify existing measures of similarity and conflict for finding LPMCSes along with quality of information heuristics to ensure that LPMCSes are formed around high-quality information. We then propose an intelligent sensor model for integrating this information into the AgentSpeak framework which is responsible for applying evidence propagation to construct compatible information, for performing context-dependent combination and for deriving beliefs for revising an agent’s belief base. Finally, we present a power grid scenario inspired by a real-world case study to demonstrate our work.

Employment regulation, game theory, and the lacuna in employee participation in liberal economies

Employee participation is a vital ingredient of what the International Labour Organization (ILO) calls ‘representation security’. This article provides theoretical and empirical insights relating to social policy impact of worker participation, specifically the European Information and Consultation Directive (ICD) for employee voice rights. While existing research on the ICD offers important empirical insights, there is a need for further theoretical analysis to examine the potential effectiveness of the regulations in liberal market economies (LMEs). Drawing on data from 16 case studies, the article uses game theory and the prisoner's dilemma framework to explain why national implementing legislation is largely ineffective in diffusing mutual gains cooperation in two LMEs: UK and the Republic of Ireland. Three theoretical (metaphorical) propositions advance understanding of the policy impact of national information & consultation regulations in LMEs.