Spontaneous Octahedral Tilting in the Cubic Inorganic Caesium Halide Perovskites CsSnX3_3 and CsPbX3_3 (X = F, Cl, Br, I)

The local crystal structures of many perovskite-structured materials deviate from the average space group symmetry. We demonstrate, from lattice-dynamics calculations based on quantum chemical force constants, that all the caesium-lead and caesium-tin halide perovskites exhibit vibrational instabilities associated with octahedral titling in their high-temperature cubic phase. Anharmonic double-well potentials are found for zone-boundary phonon modes in all compounds with barriers ranging from 108 to 512 meV. The well depth is correlated with the tolerance factor and the chemistry of the composition, but is not proportional to the imaginary harmonic phonon frequency. We provide quantitative insights into the thermodynamic driving forces and distinguish between dynamic and static disorder based on the potential-energy landscape. A positive band gap deformation (spectral blueshift) accompanies the structural distortion, with implications for understanding the performance of these materials in applications areas including solar cells and light-emitting diodes

Modeling and Analysing Respondent Driven Sampling as a Counting Process

Respondent-driven sampling (RDS) is an approach to sampling design and analysis which utilizes the networks of social relationships that connect members of the target population, using chain-referral methods to facilitate sampling. RDS typically leads to biased sampling, favoring participants with many acquaintances. Naive estimates, such as the sample average, which are uncorrected for the sampling bias, will themselves be biased. To compensate for this bias, current methodology suggests inverse-degree weighting, where the "degree" is the number of acquaintances. This stems from the fundamental RDS assumption that the probability of sampling an individual is proportional to their degree. Since this assumption is tenuous at best, we propose to harness the additional information encapsulated in the time of recruitment, into a model-based inference framework for RDS. This information is typically collected by researchers, but ignored. We adapt methods developed for inference in epidemic processes to estimate the population size, degree counts and frequencies. While providing valuable information in themselves, these quantities ultimately serve to debias other estimators, such a disease's prevalence. A fundamental advantage of our approach is that, being model-based, it makes all assumptions of the data-generating process explicit. This enables verification of the assumptions, maximum likelihood estimation, extension with covariates, and model selection. We develop asymptotic theory, proving consistency and asymptotic normality properties. We further compare these estimators to the standard inverse-degree weighting through simulations, and using real-world data. In both cases we find our estimators to outperform current methods. The likelihood problem in the model we present is convex, and thus efficiently solvable. We implement these estimators in an R package, chords, available on CRAN.Comment: 16 page

Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite

Lead halide perovskites such as methylammonium lead triiodide (MAPI) have outstanding optical and electronic properties for photovoltaic applications, yet a full understanding of how this solution processable material works so well is currently missing. Previous research has revealed that MAPI possesses multiple forms of static disorder regardless of preparation method, which is surprising in light of its excellent performance. Using high energy resolution inelastic X-ray (HERIX) scattering, we measure phonon dispersions in MAPI and find direct evidence for another form of disorder in single crystals: large amplitude anharmonic zone-edge rotational instabilities of the PbI_6 octahedra that persist to room temperature and above, left over from structural phase transitions that take place tens to hundreds of degrees below. Phonon calculations show that the orientations of the methylammonium couple strongly and cooperatively to these modes. The result is a non-centrosymmetric, instantaneous local structure, which we observe in atomic pair distribution function (PDF) measurements. This local symmetry breaking is unobservable by Bragg diffraction, but can explain key material properties such as the structural phase sequence, ultra low thermal transport, and large minority charge carrier lifetimes despite moderate carrier mobility.Comment: 30 pages, 11 figure

Geotechnical Lessons Learned From Earthquakes

Geotechnical earthquake engineering is an experience-driven discipline. Field observations are particularly important because it is difficult to replicate in the laboratory, the characteristics and response of soil deposits built by nature over thousands of years. Further, much of the data generated by a major earthquake is perishable, so it is critical that it is collected soon after the event occurs. Detailed mapping and surveying of damaged and undamaged areas provides the data for the well-documented case histories that drive the development of many of the design procedures used by geotechnical engineers. Thus, documenting the key lessons learned from major earthquake events around the world contributes significantly to advancing research and practice in geotechnical earthquake engineering. This is one of the primary objectives of the Geotechnical Extreme Events Reconnaissance (GEER) Association. Some of GEER’s findings from recent earthquakes are described in this paper. In particular, the use of advanced reconnaissance techniques is highlighted, as well as specific technical findings from the 1999 Kocaeli, Turkey earthquake, the 2007 Pisco, Peru earthquake, the 2010 Haiti earthquake, and the 2010 Maule, Chile earthquake

Microgravity Drill and Anchor System

This work is a method to drill into a rock surface regardless of the gravitational field or orientation. The required weight-on-bit (WOB) is supplied by a self-contained anchoring mechanism. The system includes a rotary percussive coring drill, forming a complete sampling instrument usable by robot or human. This method of in situ sample acquisition using micro - spine anchoring technology enables several NASA mission concepts not currently possible with existing technology, including sampling from consolidated rock on asteroids, providing a bolt network for astronauts visiting a near-Earth asteroid, and sampling from the ceilings or vertical walls of lava tubes and cliff faces on Mars. One of the most fundamental parameters of drilling is the WOB; essentially, the load applied to the bit that allows it to cut, creating a reaction force normal to the surface. In every drilling application, there is a minimum WOB that must be maintained for the system to function properly. In microgravity (asteroids and comets), even a small WOB could not be supported conventionally by the weight of the robot or astronaut. An anchoring mechanism would be needed to resist the reactions, or the robot or astronaut would push themselves off the surface and into space. The ability of the system to anchor itself to a surface creates potential applications that reach beyond use in low gravity. The use of these anchoring mechanisms as end effectors on climbing robots has the potential of vastly expanding the scope of what is considered accessible terrain. Further, because the drill is supported by its own anchor rather than by a robotic arm, the workspace is not constrained by the reach of such an arm. Yet, if the drill is on a robotic arm, it has the benefit of not reflecting the forces of drilling back to the arm s joints. Combining the drill with the anchoring feet will create a highly mobile, highly stable, and highly reliable system. The drilling system s anchor uses hundreds of microspine toes that independently find holes and ledges on a rock to create an anchor. Once the system is anchored, a linear translation mechanism moves the drill axially into the surface while maintaining the proper WOB. The linear translation mechanism is composed of a ball screw and stepper motor that can translate a carriage with high precision and applied load. The carriage slides along rails using self-aligning linear bearings that correct any axial misalignment caused by bending and torsion. The carriage then compresses a series of springs that simultaneously transmit the load to the drill along the bit axis and act as a suspension that compensates for the vibration caused by percussive drilling. The drill is a compacted, modified version of an off-the-shelf rotary percussive drill, which uses a custom carbide-tipped coring bit. By using rotary percussive drilling, the drill time is greatly reduced. The percussive action fractures the rock debris, which is removed during rotation. The final result is a 0.75-in. (.1.9- cm) diameter hole and a preserved 0.5- in. (.1.3-cm) diameter rock core. This work extends microspine technology, making it applicable to astronaut missions to asteroids and a host of robotic sampling concepts. At the time of this reporting, it is the first instrument to be demonstrated using microspine anchors, and is the first self-contained drill/anchor system to be demonstrated that is capable of drilling in inverted configurations and would be capable of drilling in microgravity

Systems and Methods for Gravity-Independent Gripping and Drilling

Systems and methods for gravity independent gripping and drilling are described. The gripping device can also comprise a drill or sampling devices for drilling and/or sampling in microgravity environments, or on vertical or inverted surfaces in environments where gravity is present. A robotic system can be connected with the gripping and drilling devices via an ankle interface adapted to distribute the forces realized from the robotic system

Simplified laboratory assessment of subgrade performance parameters for mechanistic design of pavement foundations

With the increasing agenda for sustainability, the UK is attempting to move away from the empirical design of pavement foundations to develop a performance specification approach to facilitate analytical design. For analytical design the measurement of the subgrade performance parameters of resilient modulus and resistance to permanent deformation are required. These parameters ideally need to be assessed concurrently under loading and environmental conditions similar to those the materials will experience in the field. To date, measurement of these parameters is largely confined to research laboratories using cyclic triaxial testing with advanced on sample strain measurement. This apparatus is considered too complicated for routine commercial use, hence this potentially limits the implementation of laboratory performance evaluation for routine pavement foundation design. A previous program of cyclic triaxial testing on clay subgrades indicated a series of useful correlations between strength and permanent deformation behavior (via a threshold stress), and material resilient modulus at this threshold. This paper reviews the previous work and utilizing these correlations presents data from tests on three different clay materials performed to develop simplified equipment and procedures for the routine measurement of the required design parameters. It is shown that simple pseudo-static tests can measure a subgrade modulus for a simplified performance based design. It re-evaluates the previous data (in the light of the recent work) to show a boundary correlation that may allow a shear strength based parameter to control (in design) the onset of permanent deformation, and details how long-term subgrade water content changes can be accommodated

Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal and cubic phases of methylammonium lead iodide

The hybrid halide perovskite CH3NH3PbI3 exhibits a complex structural behaviour, with successive transitions between orthorhombic, tetragonal and cubic polymorphs at ca. 165 K and 327 K. Herein we report first-principles lattice dynamics (phonon spectrum) for each phase of CH3NH3PbI3. The equilibrium structures compare well to solutions of temperature-dependent powder neutron diffraction. By following the normal modes we calculate infrared and Raman intensities of the vibrations, and compare them to the measurement of a single crystal where the Raman laser is controlled to avoid degradation of the sample. Despite a clear separation in energy between low frequency modes associated with the inorganic PbI3 network and high-frequency modes of the organic CH3NH3+ cation, significant coupling between them is found, which emphasises the interplay between molecular orientation and the corner-sharing octahedral networks in the structural transformations. Soft modes are found at the boundary of the Brillouin zone of the cubic phase, consistent with displacive instabilities and anharmonicity involving tilting of the PbI6 octahedra around room temperature.Comment: 9 pages, 4 figure