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.

Emotional responses to Hindustani raga music: the role of musical structure

In Indian classical music, ragas constitute specific combinations of tonic intervals potentially capable of evoking distinct emotions. A raga composition is typically presented in two modes, namely, alaap and gat. Alaap is the note by note delineation of a raga bound by a slow tempo, but not bound by a rhythmic cycle. Gat on the other hand is rendered at a faster tempo and follows a rhythmic cycle. Our primary objective was to (1) discriminate the emotions experienced across alaap and gat of ragas, (2) investigate the association of tonic intervals, tempo and rhythmic regularity with emotional response. 122 participants rated their experienced emotion across alaap and gat of 12 ragas. Analysis of the emotional responses revealed that (1) ragas elicit distinct emotions across the two presentation modes, and (2) specific tonic intervals are robust predictors of emotional response. Specifically, our results showed that the ‘minor second’ is a direct predictor of negative valence. (3) Tonality determines the emotion experienced for a raga where as rhythmic regularity and tempo modulate levels of arousal. Our findings provide new insights into the emotional response to Indian ragas and the impact of tempo, rhythmic regularity and tonality on it.

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.

Brain-computer music interfacing for continuous control of musical tempo

A Brain-computer music interface (BCMI) is developed to allow for continuous modification of the tempo of dynamically generated music. Six out of seven participants are able to control the BCMI at significant accuracies and their performance is observed to increase over time.

A compact low-cost electronic hardware design for actuating soft robots

A low cost, compact embedded design approach for actuating soft robots is presented. The complete fabrication procedure and mode of operation was demonstrated, and the performance of the complete system was also demonstrated by building a microcontroller based hardware system which was used to actuate a soft robot for bending motion. The actuation system including the electronic circuit board and actuation components was embedded in a 3D-printed casing to ensure a compact approach for actuating soft robots. Results show the viability of the system in actuating and controlling siliconebased soft robots to achieve bending motions. Qualitative measurements of uniaxial tensile test, bending distance and pressure were obtained. This electronic design is easy to reproduce and integrate into any specified soft robotic device requiring pneumatic actuation.

Is there a Rhythm Of The Rain? An analysis of weather in popular music

Weather is frequently used in music to frame events and emotions, yet quantitative analyses are rare. From a collated base set of 759 weather-related songs, 419 were analysed based on listings from a karaoke database. This article analyses the 20 weather types described, frequency of occurrence, genre, keys, mimicry, lyrics and songwriters. Vocals were the principal means of communicating weather: sunshine was the most common, followed by rain, with weather depictions linked to the emotions of the song. Bob Dylan, John Lennon and Paul McCartney wrote the most weather-related songs, partly following their experiences at the time of writing.

Electronic structure of Pd multi-layers on Re(0001): the role of charge transfer

Understanding the origin of the properties of metal-supported metal thin films is important for the rational design of bimetallic catalysts and other applications, but it is generally difficult to separate effects related to strain from those arising from interface interactions. Here we use density functional (DFT) theory to examine the structure and electronic behavior of few-layer palladium films on the rhenium (0001) surface, where there is negligible interfacial strain and therefore other effects can be isolated. Our DFT calculations predict stacking sequences and interlayer separations in excellent agreement with quantitative low-energy electron diffraction experiments. By theoretically simulating the Pd core-level X-ray photoemission spectra (XPS) of the films, we are able to interpret and assign the basic features of both low-resolution and high-resolution XPS measurements. The core levels at the interface shift to more negative energies, rigidly following the shifts in the same direction of the valence d-band center. We demonstrate that the valence band shift at the interface is caused by charge transfer from Re to Pd, which occurs mainly to valence states of hybridized s-p character rather than to the Pd d-band. Since the d-band filling is roughly constant, there is a correlation between the d-band center shift and its bandwidth. The resulting effect of this charge transfer on the valence d-band is thus analogous to the application of a lateral compressive strain on the adlayers. Our analysis suggests that charge transfer should be considered when describing the origin of core and valence band shifts in other metal / metal adlayer systems.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Antecedents of travellers' electronic word-of-mouth communication

Electronic word-of-mouth (eWOM) is recognised as a means of interpersonal communication and a powerful marketing tool. However, previous studies have focussed on related motivations, and limited attention has been given to understanding the antecedents of eWOM communication behaviour in the travel industry. This study proposes a full and partial mediation model, which brings together for the first time three key antecedents: adoption of electronic communication technology, consumer dis/satisfaction with travel consumption experience, and subjective norm. The model aims to understand the impact of these antecedents on travellers' attitude towards eWOM communication and intention to use eWOM communication media. The data were collected from international travellers (n = 524), and structural equation modelling is used to test the conceptual framework. The findings of the study suggest that overall attitude towards eWOM communication partially mediates the impact of the traveller's adoption of electronic communication technology and subjective norm, and fully mediates the impact of consumer dis/satisfaction with travel consumption experience on travellers' intention to use eWOM communication media.