Bond-selective energy redistribution in the chemisorption of CH3D and CD3H on Pt{1 1 0}-(1 2): a first-principles molecular dynamics study

We have investigated the chemisorption of CH3D and CD3H on Pt{11 0}-(1 2) by performing first-principles molecular dynamics simulations of the recombinative desorption of CH3D (from adsorbed methyl and deuterium) and of CD3H (from adsorbed trideuteromethyl and hydrogen). Vibrational analysis of the symmetry adapted internal coordinates of the desorbing molecules shows that excitation of the single C– D (C–H) bond in the parent molecule is strongly correlated with energy excess in the reaction coordinate. The results of the molecular dynamics simulations are consistent with observed mode- and bond-specific reactivity measurements for chemisorption of methane and its isotopomers on platinum and nickel surfaces.

The principles underlying the use of powder diffraction data in solving pharmaceutical crystal structures

Solving pharmaceutical crystal structures from powder diffraction data is discussed in terms of the methodologies that have been applied and the complexity of the structures that have been solved. The principles underlying these methodologies are summarized and representative examples of polymorph, solvate, salt and cocrystal structure solutions are provided, together with examples of some particularly challenging structure determinations.

First-principles study of the inversion thermodynamics and electronic structure of FeM2X4 (thio)spinels (M = Cr, Mn, Co, Ni; X = O, S)

FeM2X4 spinels, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for M = Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+U). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr2X4 and FeMn2S4 are fully normal, FeNi2X4 and FeCo2S4 are intermediate, and FeCo2O4 and FeMn2O4 are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr2X4, FeMn2X4, FeCo2O4 and FeNi2O4 are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When M is filling the tetrahedral positions, the Cr-containing compounds and FeMn2O4 are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn2S4. Our calculations suggest that the spin filtering properties of the FeM2X4 (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C2xB1−xN1−x alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C (x < 0.25); and (b) the electronic structure of C2xB1−xN1−x can be further tuned not only with composition x, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C2xB1−xN1−x alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

Quasi-sure existence of Gaussian rough paths and large deviation principles for capacities

We construct a quasi-sure version (in the sense of Malliavin) of geometric rough paths associated with a Gaussian process with long-time memory. As an application we establish a large deviation principle (LDP) for capacities for such Gaussian rough paths. Together with Lyons' universal limit theorem, our results yield immediately the corresponding results for pathwise solutions to stochastic differential equations driven by such Gaussian process in the sense of rough paths. Moreover, our LDP result implies the result of Yoshida on the LDP for capacities over the abstract Wiener space associated with such Gaussian process.

Logical and epistemic foundationalism about grounding: the triviality of facts and principles

In this paper, I seek to undermine G.A. Cohen’s polemical use of a metaethical claim he makes in his article, ‘Facts and Principles’, by arguing that that use requires an unsustainable equivocation between epistemic and logical grounding. I begin by distinguishing three theses that Cohen has offered during the course of his critique of Rawls and contractualism more generally, the foundationalism about grounding thesis, the justice as non-regulative thesis, and the justice as all-encompassing thesis, and briefly argue that they are analytically independent of each other. I then offer an outline of the foundationalism about grounding thesis, characterising it, as Cohen does, as a demand of logic. That thesis claims that whenever a normative principle is dependent on a fact, it is so dependent in virtue of some other principle. I then argue that although this is true as a matter of logic, it, as Cohen admits, cannot be true of actual justifications, since logic cannot tell us anything about the truth as opposed to the validity of arguments. Facts about a justification cannot then be decisive for whether or not a given argument violates the foundationalism about grounding thesis. As long as, independently of actual justifications, theorists can point to plausible logically grounding principles, as I argue contractualists can, Cohen’s thesis lacks critical bite.

'Rules of engagement’: how experiential learning facilitates the formation of a public–private partnership in Russia

Purpose – The purpose of this paper is to investigate to what extent one can apply experiential learning theory (ELT) to the public-private partnership (PPP) setting in Russia and to draw insights regarding the learning cycle ' s nature. Additionally, the paper assesses whether the PPP case confirms Kolb ' s ELT. Design/methodology/approach – The case study draws upon primary data which the authors collected by interviewing informants including a PPP operator ' s managers, lawyers from Russian law firms and an expert from the National PPP Centre. The authors accomplished data source triangulation in order to ensure a high degree of research validity. Findings – Experiential learning has resulted in a successful and a relatively fast PPP project launch without the concessionary framework. The lessons learned include the need for effective stakeholder engagement; avoiding being stuck in bureaucracy such as collaboration with Federal Ministries and anti-trust agency; avoiding application for government funding as the approval process is tangled and lengthy; attracting strategic private investors; shaping positive public perception of a PPP project; and making continuous efforts in order to effectively mitigate the public acceptance risk. Originality/value – The paper contributes to ELT by incorporating the impact of social environment in the learning model. Additionally, the paper tests the applicability of ELT to learning in the complex organisational setting, i.e., a PPP.

Legal and regulatory barriers to effective public-private partnership governance in Kazakhstan

Purpose – The purpose of this paper is to provide a critical assessment of legal and regulatory impediments to effective governance of public-private partnerships (PPPs) in Kazakhstan. Design/methodology/approach – The qualitative study develops propositions from the PPP literature and then tests them against findings from in-depth interviews. Interviewees have been selected by a purposeful sampling from PPP projects in Kazakhstan as well as from national and regional PPP centres. Findings – The identified barriers to effective PPP management include irregularities in the PPP legal framework, such as lack of legal definition of a PPP and controversy with the government guarantee’s legal status for its long-term payments to partnerships; bureaucratic tariff setting for partnership services; non-existent opportunity for private asset ownership; and excessive government regulation of PPP workers’ wage rates. Practical implications – The partners’ opposing perspectives on a number of PPP issues show that management needs to identify and carefully reconcile stakeholder values in a partnership in order to achieve more effective PPP governance. Practitioners, particularly those in the public agencies, have to be concerned with ways to reduce the government overregulation of the private operators, which is likely to result in greater PPP flexibility in management and, ultimately, higher efficiency in delivering the public services. Originality/value – By elucidating multiple examples of overregulation and PPPs’ inefficiency, the paper demonstrates that the government dominance in PPP management is conceptually inappropriate. Instead, the government should adopt the concept of co-production and manage its relations with the private sector partner in a collaborative fashion.

Measuring the economic value of pollination services: principles, evidence and knowledge gaps

An increasing degree of attention is being given to the ecosystem services which insect pollinators supply, and the economic value of these services. Recent research suggests that a range of factors are contributing to a global decline in pollination services, which are often used as a “headline” ecosystem service in terms of communicating the concept of ecosystem services, and how this ties peoples׳ well-being to the condition of ecosystems and the biodiversity found therein. Our paper offers a conceptual framework for measuring the economic value of changes in insect pollinator populations, and then reviews what evidence exists on the empirical magnitude of these values (both market and non-market). This allows us to highlight where the largest gaps in knowledge are, where the greatest conceptual and empirical challenges remain, and where research is most needed.

Typo-resource: developing T&L support materials through collaboration

This paper reports on a collaborative project between staff and students in the Department of Typography & Graphic Communication at the University of Reading The Partnerships in Learning and Teaching (PLanT) project here described is a direct response to student needs for better online support materials. Methodologically, the project embeds user-centred design principles within an iterative process of design development and participant research. This process has underpinned the development of a prototype for an online interface called Typo-Resource. The resulting initial prototype addresses the usability and user experience dimensions of an online learning resource, moving beyond providing tutor-identified sets of resources to a multifaceted, collaborative, and visual platform for peer learning.