Mode-specific chemisorption of CH4 on Pt{110}-(1 x 2) explored by first-principles molecular dynamics

The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability

The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study

Sulphide materials, in particular MoS2, have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS2) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the FeS2(100) surface. Our results show that both those environmentally important NOx species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO2 adsorption onto one of the non-equivalent Fe–Fe bridge sites of the (1 1)–FeS2(100) surface. From the calculated high barrier for NO and NO2 direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

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.

Preliminary leaf area index estimates from airborne small footprint full-waveform LiDAR data

This study has compared preliminary estimates of effective leaf area index (LAI) derived from fish-eye lens photographs to those estimated from airborne full-waveform small-footprint LiDAR data for a forest dataset in Australia. The full-waveform data was decomposed and optimized using a trust-region-reflective algorithm to extract denser point clouds. LAI LiDAR estimates were derived in two ways (1) from the probability of discrete pulses reaching the ground without being intercepted (point method) and (2) from raw waveform canopy height profile processing adapted to small-footprint laser altimetry (waveform method) accounting for reflectance ratio between vegetation and ground. The best results, that matched hemispherical photography estimates, were achieved for the waveform method with a study area-adjusted reflectance ratio of 0.4 (RMSE of 0.15 and 0.03 at plot and site level, respectively). The point method generally overestimated, whereas the waveform method with an arbitrary reflectance ratio of 0.5 underestimated the fish-eye lens LAI estimates.

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.

Bioethics through the telescope: institutional ethics in the NHS

The article argues for a broader conception of bioethics. The principles that dominate current thinking are generally individualistic and do not represent the real world inhabited by patients, doctors, hospitals and the NHS as a whole. Rather than focus almost exclusively on the micro-end of the analytical spectrum, bioethics, and medical lawyers in particular, should take the institutional dimensions of health and health care more seriously, ie use a telescope to understand the dynamics that drive the subject, not just a microscope.

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.

Ethics education in management accounting studies: evidence from business schools in Ghana

Management accounting in recent times, and perhaps rightly so, has begun to gain recognition as a profession separate and complimentary to financial accounting. Evidence exists to suggest that management accountants are exposed to a unique set of ethical challenges within industry and that a significant high number of management accountants have engaged in unethical practices in performing their jobs. For the accounting profession as a whole, the growing number of corporate failures has created a credibility crisis that requires a deliberate intervention to mitigate. If this is not addressed sooner, the accounting profession stands the risk of losing relevance. Scholarship on ethical issues in accounting practice have either focused mostly on financial accounting or have sought to combine ethical issues for financial and management accounting. Various arguments have been made in recent times of the need to treat ethical issues in behavioural studies as context-specific and therefore separate ethical considerations in management accounting from financial accounting. This study adopts an approach, following various literature, that effective ethics education can help practitioners deal appropriately with ethical issues at the work place, and explores students’ and faculty members’perceptions on current practices in ethics education. As expected, faculty and students differ significantly on a wide range of issues on ethics education in management accounting. Based on the insights provided from this study, appropriate recommendations have been made to improve ethics education in management accounting.

Influence of individual ethical orientation on tax compliance: evidence among Ghanaian taxpayers

Even though Africa has constantly emphasized the need to reduce deficit financing through mobilization of more internal revenues, this has not been achieved. Perhaps encouraging voluntary tax compliance can improve internal revenue mobilization. This study explores the relationship between ethical orientation and tax compliance and finds that ethical persons are generally more tax compliant than unethical persons but are more influenced by considerations of tax rate and withholding positions compared to unethical persons. The findings of this study differ from Reckers et al. in a number of ways and contribute to the literature by providing a possible explanation of the cause(s) of tax non- compliance.

IFRS for SMEs: the IASB’S due process

This study explores the role of the International Accounting Standards Board’s (IASB) due process in developing its International Financial Reporting Standards for Small and Medium-sized Entities (IFRS or SMEs)standard. There were tensions between the IASB’s desire to minimise divergence from full IFRS and preserve recognition and measurement principles, and the primary reasons for undertaking the project – to meet the needs of users of financial statements of SMEs and to reduce the financial reporting burden on SMEs. Examination of events during the development of the project reveals much that was not apparent from material in the public domain. Most significantly, the IASB recognised that the final title of the standard, IFRS for SMEs, does not necessarily describe the scope of the standard. This paper also shows that the due process followed in the case of the IFRS for SMEs project barely reflected the ‘will of people’ but was more inclined towards acting as a communicative function for the IASB without any commitment to change its stance on the SME standard.

PLEASE CITE THIS: an exploratory paper on citations, impacts and the social accounting literature

This paper seeks to use the increasingly influential citation and impact data to explore the contours of the social and environmental accounting (SEA) literature. Our ambitions are fourfold. First, we offer a more nuanced understanding of the journals in which we tend to publish SEA research. Second, we tease out what might plausibly be thought to be one indication of the ‘most influential’ SEA papers. Third, we offer a substantive cautionary note about the dangers of the careless use of citations as singular measures of ‘quality’ or ‘importance’, etc. Finally, we place the growing SEA literature in a wider context which both flatters and challenges the community that SEAJ seeks to serve.