Critical properties of the unconventional spin-Peierls system TiOBr

We have performed detailed x-ray scattering measurements on single crystals of the spin-Peierls compound TiOBr in order to study the critical properties of the transition between the incommensurate spin-Peierls state and the paramagnetic state at Tc2 ~ 48 K. We have determined a value of the critical exponent beta which is consistent with the conventional 3D universality classes, in contrast with earlier results reported for TiOBr and TiOCl. Using a simple power law fit function we demonstrate that the asymptotic critical regime in TiOBr is quite narrow, and obtain a value of beta_{asy} = 0.32 +/- 0.03 in the asymptotic limit. A power law fit function which includes the first order correction-to-scaling confluent singularity term can be used to account for data outside the asymptotic regime, yielding a more robust value of beta_{avg} = 0.39 +/- 0.05. We observe no evidence of commensurate fluctuations above Tc1 in TiOBr, unlike its isostructural sister compound TiOCl. In addition, we find that the incommensurate structure between Tc1 and Tc2 is shifted in Q-space relative to the commensurate structure below Tc1.Comment: 12 pages, 8 figures. Submitted to Physical Review

Commensurate Fluctuations in the Pseudogap and Incommensurate spin-Peierls Phases of TiOCl

X-ray scattering measurements on single crystals of TiOCl reveal the presence of commensurate dimerization peaks within both the incommensurate spin-Peierls phase and the so-called pseudogap phase above T_c2. This scattering is relatively narrow in Q-space indicating long correlation lengths exceeding ~ 100 A below T* ~ 130 K. It is also slightly shifted in Q relative to that of the commensurate long range ordered state at the lowest temperatures, and it coexists with the incommensurate Bragg peaks below T_c2. The integrated scattering over both commensurate and incommensurate positions evolves continuously with decreasing temperature for all temperatures below T* ~ 130 K.Comment: To appear in Physical Review B: Rapid Communications. 5 page

Suppression of the commensurate spin-Peierls state in Sc-doped TiOCl

We have performed x-ray scattering measurements on single crystals of the doped spin-Peierls compound Ti(1-x)Sc(x)OCl (x = 0, 0.01, 0.03). These measurements reveal that the presence of non-magnetic dopants has a profound effect on the unconventional spin-Peierls behavior of this system, even at concentrations as low as 1%. Sc-doping suppresses commensurate fluctuations in the pseudogap and incommensurate spin-Peierls phases of TiOCl, and prevents the formation of a long-range ordered spin-Peierls state. Broad incommensurate scattering develops in the doped compounds near Tc2 ~ 93 K, and persists down to base temperature (~ 7 K) with no evidence of a lock-in transition. The width of the incommensurate dimerization peaks indicates short correlation lengths on the order of ~ 12 angstroms below Tc2. The intensity of the incommensurate scattering is significantly reduced at higher Sc concentrations, indicating that the size of the associated lattice displacement decreases rapidly as a function of doping.Comment: 7 pages, 5 figure

Singlet-Triplet Excitations in the Unconventional Spin-Peierls System TiOBr

We have performed time-of-flight neutron scattering measurements on powder samples of the unconventional spin-Peierls compound TiOBr using the fine-resolution Fermi chopper spectrometer (SEQUOIA) at the SNS. These measurements reveal two branches of magnetic excitations within the commensurate and incommensurate spin-Peierls phases, which we associate with n = 1 and n = 2 triplet excitations out of the singlet ground state. These measurements represent the first direct measure of the singlet-triplet energy gap in TiOBr, which is determined to be Eg = 21.2 +/- 1.0 meV.Comment: 5 pages, 4 figures, submitted for publicatio

Recovery of surface reflectance spectra and evaluation of the optical depth of aerosols in the near-IR using a Monte-Carlo approach: Application to the OMEGA observations of high latitude regions of Mars

We present a model of radiative transfer through atmospheric particles based on Monte Carlo methods. This model can be used to analyze and remove the contribution of aerosols in remote sensing observations. We have developed a method to quantify the contribution of atmospheric dust in near-IR spectra of the Martian surface obtained by the OMEGA imaging spectrometer on board Mars Express. Using observations in the nadir pointing mode with significant differences in solar incidence angles, we can infer the optical depth of atmospheric dust, and we can retrieve the surface reflectance spectra free of aerosol contribution. Martian airborne dust properties are discussed and constrained from previous studies and OMEGA data. We have tested our method on a region at 90{\deg}E and 77{\deg}N extensively covered by OMEGA, where significant variations of the albedo of ice patches in the visible have been reported. The consistency between reflectance spectra of ice-covered and ice-free regions recovered at different incidence angles validates our approach. The optical depth of aerosols varies by a factor 3 in this region during the summer of Martian year 27. The observed brightening of ice patches does not result from frost deposition but from a decrease in the dust contamination of surface ice and (to a lower extent) from a decrease in the optical thickness of atmospheric dust. Our Monte Carlo-based model can be applied to recover the spectral reflectance characteristics of the surface from OMEGA spectral imaging data when the optical thickness of aerosols can be evaluated. It could prove useful for processing image cubes from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on board the Mars Reconnaissance Orbiter (MRO)

Catalogue of extreme wave events in Ireland: revised and updated for 14680 BP - 2017

This paper aims to extend and update the survey of extreme wave events in Ireland that was previously carried out by O’Brien et al. (2013). The original catalogue highlighted the frequency of such events dating back as far as the turn of the last ice age through to 2012. Ireland’s marine territory extends far beyond its coastline and is one of the largest seabed territories in Europe. It is therefore not surprising that extreme waves have continued to occur regularly since 2012, particularly considering the severity of weather during the winters of 2013-14 and 2015-16. In addition, a large number of storm surges have been identified since the publication of the original catalogue. This paper updates the O’Brien et al. (2013) catalogue to include events up to the end of 2016. Storm surges are included as a new category and events are categorised into long waves (tsunamis and storm surges) and short waves (storm and rogue waves). New results prior to 2012 are also included and some of the events previously documented are reclassified. Important questions regarding public safety, services and the influence of climate change are also highlighted

The structure of liquid thiophene from total neutron scattering

The structure of pure liquid thiophene is revealed by using a combination of total neutron scattering experiments with isotopic substitution and molecular simulations via the next generation empirical potential refinement software, Dissolve. In the liquid, thiophene presents three principle local structural motifs within the first solvation shell, in plane and out of the plane of the thiophene ring. Firstly, above/below the ring plane thiophenes present a single H towards the π cloud, due to a combination of electrostatic and dispersion interactions. Secondly, around the ring plane, perpendicular thiophene molecules find 5 preferred sites driven by bifurcated C-H⋯S interactions, showing that hydrogen-sulfur bonding prevails over the charge asymmetry created by the heteroatom. Finally, parallel thiophenes sit above and below the ring, excluded from directly above the ring center and above the sulfur

New functionalisation reactions of graphitic carbon nitrides: Computational and experimental studies

The functionalisation of two-dimensional materials is key to modify their properties and facilitate assembly into functional devices. Here, new reactions have been proposed to modify crystalline two-dimensional carbon nitrides of polytriazine imide structure. Both amine alkylation and aryl-nitrene-based reactions have been explored computationally and with exploratory synthetic trials. The approach illustrates that alkylation is unfavourable, particularly at basal-plane sites. In contrast, while initial trial reactions were inconclusive, the radical-addition of nitrenes is shown to be energetically favourable, with a preference for functionalising sheet edges to minimise steric effects