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Entropy is a critical, but often overlooked, factor in determining the relative stabilities of crystal phases. The importance of entropy is most pronounced in softer materials, where small changes in free energy can drive phase transitions, which has recently been demonstrated in the case of organic-inorganic hybrid-formate perovskites. In this study we demonstrate the interplay between composition and crystal-structure that is responsible for the particularly pronounced role of entropy in determining polymorphism in hybrid organic-inorganic materials. Using ab initio based lattice dynamics we probe the origins and effects of vibrational entropy of four archetype perovskite (ABX$_3$) structures. We consider a fully inorganic material (SrTiO$_3$), an A-site hybrid halide material (CH$_3$NH$_3$PbI$_3$), an X-site hybrid material (KSr(BH$_4$)$_3$) and a mixed A- and X-site hybrid-formate material (N$_2$H$_5$Zn(HCO$_2$)$_3$), comparing the differences in entropy between two common polymorphs. The results demonstrate the importance of low-frequency inter-molecular modes in determining phase stability in these materials. The understanding gained allows us to propose a general principle for the relative stability of different polymorphs of hybrid materials as temperature is increased.

Density functional theory screening of the hybrid double perovskites (MA)2BIBiX6 (BI=K,Cu,Ag,Tl; X=Cl,Br,I) shows that systems with band gaps similar to those of the MAPbX3 lead compounds can be expected for BI=Cu,Ag,Tl. Motivated by these findings, (MA)2TlBiBr6, isoelectronic with MAPbBr3, was synthesised and found to have a band gap of ~2.0eV.

In a search for Lead-free materials that could be used as alternatives to the hybrid perovskites,(MA)PbX3, in photovoltaic applications, we have discovered a hybrid double perovskite, (MA)2KBiCl6, which shows striking similarities to the lead analogues. Spectroscopic measurements and nanoindentation studies are combined with density functional calculations to reveal the properties of this interesting system.

We image with unprecedented spatial resolution and sensitivity disk features that could be potential signs of planet-disk interaction. Two companion candidates have been claimed in the disk around the young Herbig Ae/Be star HD100546. Thus, this object serves as an excellent target for our investigation of the natal environment of giant planets. We exploit the power of extreme adaptive optics operating in conjunction with the new high-contrast imager SPHERE to image HD100546 in scattered light. We obtain the first polarized light observations of this source in the visible (with resolution as fine as 2 AU) and new H and K band total intensity images that we analyze with the Pynpoint package. The disk shows a complex azimuthal morphology, where multiple scattering of photons most likely plays an important role. High brightness contrasts and arm-like structures are ubiquitous in the disk. A double-wing structure (partly due to ADI processing) resembles a morphology newly observed in inclined disks. Given the cavity size in the visible (11 AU), the CO emission associated to the planet candidate 'c' might arise from within the circumstellar disk. We find an extended emission in the K band at the expected location of 'b'. The surrounding large-scale region is the brightest in scattered light. There is no sign of any disk gap associated to 'b'., Comment: Accepted by A&A. 13 pages, 5 figures

Organic-inorganic halide perovskites, especially methylammonium lead halide, have recently led to a remarkable breakthrough in photovoltaic devices. However, due to the environmental and stability concerns of the heavy metal, lead, in these perovskite based solar cells, research in the non-lead perovskite structures have been attracting increasing attention. In this study, a layered perovskite-like architecture, (NH4)3Bi2I9, was prepared in solution and the structure was solved by single crystal X-ray diffraction. The results from DFT calculations showed the significant lone pair effect of the bismuth ion and the band gap was measured as around 2.04 eV, which is lower than the band gap of CH3NH3PbBr3. Conductivity measurement was also performed to examine the potential in the applications as an alternative to the lead containing perovskites.

We conduct a multiplicity survey of members of the rho Ophiuchus cloud complex with high resolution imaging to characterize the multiple star population of this nearby star forming region and investigate the relation between stellar multiplicity and star and planet formation. Our aperture masking survey reveals the presence of 5 new stellar companions beyond the reach of previous studies, but does not result in the detection of any new substellar companions. We find that 43+/-6% of the 114 stars in our survey have stellar mass companions between 1.3-780AU, while 7 (+8 -5)% host brown dwarf companions in the same interval. By combining this information with knowledge of disk-hosting stars, we show that the presence of a close binary companion (separation < 40 AU) significantly influences the lifetime of protoplanetary disks, a phenomenon previously seen in older star forming regions. At the ~1-2Myr age of our Ophiuchus members ~2/3 of close binary systems have lost their disks, compared to only ~30% of single stars and wide binaries. This has significant impact on the formation of giant planets, which are expected to require much longer than 1 Myr to form via core accretion and thus planets formed via this pathway should be rare in close binary systems., Comment: 17 pages, 8 figures, 4 tables. Accepted for publication in ApJ

We report the detection of seven low mass companions to intermediate-mass stars (SpT B/A/F; $M$$\approx$1.5-4.5 solar masses) in the Scorpius-Centaurus Association using nonredundant aperture masking interferometry. Our newly detected objects have contrasts $\Delta L'$$\approx$4-6, corresponding to masses as low as $\sim$20 Jupiter masses and mass ratios of $q$$\approx$0.01-0.08, depending on the assumed age of the target stars. With projected separations $\rho$$\approx$10-30 AU, our aperture masking detections sample an orbital region previously unprobed by conventional adaptive optics imaging of intermediate mass Scorpius-Centaurus stars covering much larger orbital radii ($\approx$30-3000 AU). At such orbital separations, these objects resemble higher mass versions of the directly imaged planetary mass companions to the 10-30 Myr, intermediate-mass stars HR 8799, $\beta$ Pictoris, and HD95086. These newly discovered companions span the brown dwarf desert, and their masses and orbital radii provide a new constraint on models of the formation of low-mass stellar and substellar companions to intermediate-mass stars., Comment: Accepted for Publication in ApJ Letters

The Gemini Planet Imager (GPI) Extreme Adaptive Optics Coronograph contains an interferometric mode: a 10-hole non-redundant mask (NRM) in its pupil wheel. GPI operates at $Y, J, H$, and $K$ bands, using an integral field unit spectrograph (IFS) to obtain spectral data at every image pixel. NRM on GPI is capable of imaging with a half resolution element inner working angle at moderate contrast, probing the region behind the coronagraphic spot. The fine features of the NRM PSF can provide a reliable check on the plate scale, while also acting as an attenuator for spectral standard calibrators that would otherwise saturate the full pupil. NRM commissioning data provides details about wavefront error in the optics as well as operations of adaptive optics control without pointing control from the calibration system. We compare lab and on-sky results to evaluate systematic instrument properties and examine the stability data in consecutive exposures. We discuss early on-sky performance, comparing images from integration and tests with the first on-sky images, and demonstrate resolving a known binary. We discuss the status of NRM and implications for future science with this mode., Comment: 14 pages, 14 figures. Proceedings of the SPIE, 9147-135

In astronomy and microscopy, distortions in the wavefront affect the dynamic range of a high contrast imaging system. These aberrations are either imposed by a turbulent medium such as the atmosphere, by static or thermal aberrations in the optical path, or by imperfectly phased subapertures in a segmented mirror. Active and adaptive optics (AO), consisting of a wavefront sensor and a deformable mirror, are employed to address this problem. Nevertheless, the non-common-path between the wavefront sensor and the science camera leads to persistent quasi-static speckles that are difficult to calibrate and which impose a floor on the image contrast. In this paper we present the first experimental demonstration of a novel wavefront sensor requiring only a minor asymmetric obscuration of the pupil, using the science camera itself to detect high order wavefront errors from the speckle pattern produced. We apply this to correct errors imposed on a deformable microelectromechanical (MEMS) segmented mirror in a closed loop, restoring a high quality point spread function (PSF) and residual wavefront errors of order $\sim 10$ nm using 1600 nm light, from a starting point of $\sim 300$ nm in piston and $\sim 0.3$ mrad in tip-tilt. We recommend this as a method for measuring the non-common-path error in AO-equipped ground based telescopes, as well as as an approach to phasing difficult segmented mirrors such as on the \emph{James Webb Space Telescope} primary and as a future direction for extreme adaptive optics., Comment: 9 pages, 6 figures

The local nuclear and magnetic structure of wustite, Fe1-xO, and the coupling between them, has been examined using reverse Monte Carlo refinements of variable-temperature neutron total scattering data. The results from this analysis suggest that the individual units in a tetrahedral defect cluster are connected along <110> vectors into a Koch-Cohen-like arrangement, with the majority of octahedral vacancies concentrated near these defects. Bond valence calculations indicate a change in the charge distribution on the cations with the charge on the tetrahedral interstitials increasing on cooling. The magnetic structure is more complex than previously thought, corresponding to a non-collinear spin arrangement described by a superposition of a condensed spin wave on the established type-II antiferromagnetic ordering. This leads to an architecture with four groups of cations each with different spin directions. The cations within the interstitial clusters appear to be weakly ferromagnetically coupled and their spins are correlated to the spins of the octahedral cations closest to them. This work not only provides further insight into the local structure of wustite but also a better understanding of the coupling between defect structures and magnetic and charge-ordering in complex materials., Comment: 9 pages, 8 figures

This paper presents an overview of recent progress at the Sydney University Stellar Interferometer (SUSI). Development of the third-generation PAVO beam combiner has continued. The MUSCA beam combiner for high-precision differential astrometry using visible light phase referencing is under active development and will be the subject of a separate paper. Because SUSI was one of the pioneering interferometric instruments, some of its original systems are old and have become difficult to maintain. We are undertaking a campaign of modernization of systems: (1) an upgrade of the Optical Path Length Compensator IR laser metrology counter electronics from a custom system which uses an obsolete single-board computer to a modern one based on an FPGA interfaced to a Linux computer - in addition to improving maintainability, this upgrade should allow smoother motion and higher carriage speeds; (2) the replacement of the aged single-board computer local controllers for the siderostats and the longitudinal dispersion compensator has been completed; (3) the large beam reducing telescope has been replaced with a pair of smaller units with separate accessible foci. Examples of scientific results are also included., Comment: 10 pages, 9 Figures

We show that ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal--amorphous transition on heating to 300 $^\circ$C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 $^\circ$C. Neutron and X-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. We show that the structure is best understood in terms of a continuous random network analogous to that of a-SiO$_2$. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glass-like phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glass-like materials that exploit the chemical and structural diversity of MOFs., Comment: 4 pages, formatted for PRL

Time-of-flight neutron powder diffraction and specific heat measurements were used to study the nature of thermal expansion in rhenium trioxide, an electrically conducting oxide with cubic symmetry. The temperature evolution of the lattice parameters show that ReO3 can exhibit negative thermal expansion at low temperatures and that the transition from negative to positive thermal expansion depends on sample preparation; the single crystal sample demonstrated the highest transition temperature, 300 K, and largest negative value for the coefficient of thermal expansion, alpha = -1.1(1)x 10^-6 K^-1. For the oxygen atoms, the atomic displacement parameters are strongly anisotropic even at 15 K, indicative of a large contribution of static disorder to the displacement parameters. Further inspection of the temperature evolution of the oxygen displacement parameters for different samples reveals that the static disorder contribution is greater for the samples with diminished NTE behavior. In addition, specific heat measurements show that ReO3 lacks the low energy Einstein-type modes seen in other negative thermal expansion oxides such as ZrW2O8., Comment: 6 pages, 5 figures

Near or less than 10% Nb substitution on the Ti site in perovskite SrTiO$_3$ results in metallic behavior, in contrast to what is seen in BaTiO$_3$. Given the nearly identical structure and electron counts of the two materials, the distinct ground states for low substitution have been a long-standing puzzle. Here we find from neutron studies of average and local structure, the subtle yet critical difference that we believe underpins the distinct electronic properties in these fascinating materials. While SrTi$_{0.875}$Nb_${0.125}$O$_3$ possesses a distorted non-cubic structure at 15 K, the BO$_6$ octahedra in the structure are regular. BaTi$_{0.875}$Nb$_{0.125}$O$_3$ on the other hand shows evidence for local cation off-centering whilst retaining a cubic structure., Comment: 4 pages, 5 figures