Solvent promoted reversible cyclometalation in a tethered NHC iridium complex

Reaction of [Ir(COD)(py–ItBu)]+ (py–ItBu = 3-tert-butyl-1-picolylimidazol-2-ylidene) with acetonitrile results in reversible intramolecular C–H bond activation of the NHC ligand and formation of [Ir(η2:η1-C8H13)(py–ItBu′)(NCMe)]+. Coordinated COD acts as an internal hydride acceptor and acetonitrile coordination offsets the otherwise unfavourable thermodynamics of the process

Defendants with intellectual disability and autism spectrum conditions the perspective of clinicians working across three jurisdictions

The treatment of vulnerable defendants by criminal justice systems or correctional systems varies within and between countries. The purpose of this paper is to examine three legal jurisdictions – New South Wales in Australia; Norway; England and Wales – to understand the extent of variation in practice within the court systems for defendants with intellectual disabilities (ID) and/or autism spectrum conditions (ASC). Two of the jurisdictions had a process for screening in place, either in police custody or at court, but this was not universally implemented across each jurisdiction. All three jurisdictions had a process for supporting vulnerable defendants through the legal system. Across the three jurisdictions, there was variation in disposal options from a mandatory care setting to hospital treatment to a custodial sentence for serious offences. This variation requires further international exploration to ensure the rights of defendants with ID or ASC are understood and safeguarde

Solar-like oscillations with low amplitude in the CoRoT target HD 181906

Context: The F8 star HD 181906 (effective temperature ~6300K) was observed for 156 days by the CoRoT satellite during the first long run in the centre direction. Analysis of the data reveals a spectrum of solar-like acoustic oscillations. However, the faintness of the target (m_v=7.65) means the signal-to-noise (S/N) in the acoustic modes is quite low, and this low S/N leads to complications in the analysis. Aims: To extract global variables of the star as well as key parameters of the p modes observed in the power spectrum of the lightcurve. Methods: The power spectrum of the lightcurve, a wavelet transform and spot fitting have been used to obtain the average rotation rate of the star and its inclination angle. Then, the autocorrelation of the power spectrum and the power spectrum of the power spectrum were used to properly determine the large separation. Finally, estimations of the mode parameters have been done by maximizing the likelihood of a global fit, where several modes were fit simultaneously. Results: We have been able to infer the mean surface rotation rate of the star (~4 microHz) with indications of the presence of surface differential rotation, the large separation of the p modes (~87 microHz), and therefore also the ridges corresponding to overtones of the acoustic modes.Comment: Paper Accepted to be published in A&A. 10 Pages, 12 figure

Potassium binding adjacent to cationic transition metal fragments: unusual heterobimetallic adducts of a calix[4]arene-based thione ligand

The synthesis of cationic rhodium and iridium complexes of a bis(imidazol-2-thione) functionalised calix[4]arene ligand and their surprising capacity for potassium binding is described. In both cases uptake of the alkali metal into the calix[4]arene cavity occurs despite adverse electrostatic interactions associated with close proximity to the transition metal fragment (Rh+∙∙∙K+ = 3.715(1) Å, Ir+∙∙∙K+ = 3.690(1) Å). The formation and constituent bonding of these unusual heterobimetallic adducts has been interrogated through extensive solution and solid-state characterisation, examination of the host-guest chemistry of the ligand and its upper-rim unfunctionalised calix[4]arene analogue, and computationally using DFT-based energy decomposition analysis (EDA)

Global asteroseismic properties of solar-like oscillations observed by Kepler : A comparison of complementary analysis methods

We present the asteroseismic analysis of 1948 F-, G- and K-type main-sequence and subgiant stars observed by the NASA {\em Kepler Mission}. We detect and characterise solar-like oscillations in 642 of these stars. This represents the largest cohort of main-sequence and subgiant solar-like oscillators observed to date. The photometric observations are analysed using the methods developed by nine independent research teams. The results are combined to validate the determined global asteroseismic parameters and calculate the relative precision by which the parameters can be obtained. We correlate the relative number of detected solar-like oscillators with stellar parameters from the {\em Kepler Input Catalog} and find a deficiency for stars with effective temperatures in the range $5300 \lesssim T_\mathrm{eff} \lesssim 5700$\,K and a drop-off in detected oscillations in stars approaching the red edge of the classical instability strip. We compare the power-law relationships between the frequency of peak power, $\nu_\mathrm{max}$, the mean large frequency separation, $\Delta\nu$, and the maximum mode amplitude, $A_\mathrm{max}$, and show that there are significant method-dependent differences in the results obtained. This illustrates the need for multiple complementary analysis methods to be used to assess the robustness and reproducibility of results derived from global asteroseismic parameters.Comment: 14 pages, 9 figures, accepted for publication in Monthly Notices of the Royal Astronomical Societ

Solar-like oscillations in KIC11395018 and KIC11234888 from 8 months of Kepler data

We analyze the photometric short-cadence data obtained with the Kepler Mission during the first eight months of observations of two solar-type stars of spectral types G and F: KIC 11395018 and KIC 11234888 respectively, the latter having a lower signal-to-noise ratio compared to the former. We estimate global parameters of the acoustic (p) modes such as the average large and small frequency separations, the frequency of the maximum of the p-mode envelope and the average linewidth of the acoustic modes. We were able to identify and to measure 22 p-mode frequencies for the first star and 16 for the second one even though the signal-to-noise ratios of these stars are rather low. We also derive some information about the stellar rotation periods from the analyses of the low-frequency parts of the power spectral densities. A model-independent estimation of the mean density, mass and radius are obtained using the scaling laws. We emphasize the importance of continued observations for the stars with low signal-to-noise ratio for an improved characterization of the oscillation modes. Our results offer a preview of what will be possible for many stars with the long data sets obtained during the remainder of the mission.Comment: 39 pages, 9 figures. Accepted for publication in Ap

Asteroseismology from multi-month Kepler photometry: the evolved Sun-like stars KIC 10273246 and KIC 10920273

The evolved main-sequence Sun-like stars KIC 10273246 (F-type) and KIC 10920273 (G-type) were observed with the NASA Kepler satellite for approximately ten months with a duty cycle in excess of 90%. Such continuous and long observations are unprecedented for solar-type stars other than the Sun. We aimed mainly at extracting estimates of p-mode frequencies - as well as of other individual mode parameters - from the power spectra of the light curves of both stars, thus providing scope for a full seismic characterization. The light curves were corrected for instrumental effects in a manner independent of the Kepler Science Pipeline. Estimation of individual mode parameters was based both on the maximization of the likelihood of a model describing the power spectrum and on a classic prewhitening method. Finally, we employed a procedure for selecting frequency lists to be used in stellar modeling. A total of 30 and 21 modes of degree l=0,1,2 - spanning at least eight radial orders - have been identified for KIC 10273246 and KIC 10920273, respectively. Two avoided crossings (l=1 ridge) have been identified for KIC 10273246, whereas one avoided crossing plus another likely one have been identified for KIC 10920273. Good agreement is found between observed and predicted mode amplitudes for the F-type star KIC 10273246, based on a revised scaling relation. Estimates are given of the rotational periods, the parameters describing stellar granulation and the global asteroseismic parameters $\Delta\nu$ and $\nu_{\rm{max}}$.Comment: 15 pages, 15 figures, to be published in Astronomy & Astrophysic

Probing the core structure and evolution of red giants using gravity-dominated mixed modes observed with Kepler

We report for the first time a parametric fit to the pattern of the \ell = 1 mixed modes in red giants, which is a powerful tool to identify gravity-dominated mixed modes. With these modes, which share the characteristics of pressure and gravity modes, we are able to probe directly the helium core and the surrounding shell where hydrogen is burning. We propose two ways for describing the so-called mode bumping that affects the frequencies of the mixed modes. Firstly, a phenomenological approach is used to describe the main features of the mode bumping. Alternatively, a quasi-asymptotic mixed-mode relation provides a powerful link between seismic observations and the stellar interior structure. We used period \'echelle diagrams to emphasize the detection of the gravity-dominated mixed modes. The asymptotic relation for mixed modes is confirmed. It allows us to measure the gravity-mode period spacings in more than two hundred red giant stars. The identification of the gravity-dominated mixed modes allows us to complete the identification of all major peaks in a red giant oscillation spectrum, with significant consequences for the true identification of \ell = 3 modes, of \ell = 2 mixed modes, for the mode widths and amplitudes, and for the \ell = 1 rotational splittings. The accurate measurement of the gravity-mode period spacing provides an effective probe of the inner, g-mode cavity. The derived value of the coupling coefficient between the cavities is different for red giant branch and clump stars. This provides a probe of the hydrogen-shell burning region that surrounds the helium core. Core contraction as red giants ascend the red giant branch can be explored using the variation of the gravity-mode spacing as a function of the mean large separation.Comment: Accepted in A&