Characterization of Singlet Ground and Low-Lying Electronic Excited States of Phosphaethyne and Isophosphaethyne

The singlet ground _X˜ 1_+_ and excited _1_− , 1__ states of HCP and HPC have been systematically investigated using ab initio molecular electronic structure theory. For the ground state, geometries of the two linear stationary points have been optimized and physical properties have been predicted utilizing restricted self-consistent field theory, coupled cluster theory with single and double excitations _CCSD_, CCSD with perturbative triple corrections _CCSD_T__, and CCSD with partial iterative triple excitations _CCSDT-3 and CC3_. Physical properties computed for the global minimum _X˜ 1_+HCP_ include harmonic vibrational frequencies with the cc-pV5Z CCSD_T_ method of _1=3344 cm−1, _2=689 cm−1, and _3=1298 cm−1. Linear HPC, a stationary point of Hessian index 2, is predicted to lie 75.2 kcal mol−1 above the global minimum HCP. The dissociation energy D0_HCP_X˜ 1_+_→H_2S_+CP_X 2_+__ of HCP is predicted to be 119.0 kcal mol−1, which is very close to the experimental lower limit of 119.1 kcal mol−1. Eight singlet excited states were examined and their physical properties were determined employing three equation-of-motion coupled cluster methods _EOM-CCSD, EOM-CCSDT-3, and EOM-CC3_. Four stationary points were located on the lowest-lying excited state potential energy surface, 1_− →1A_, with excitation energies Te of 101.4 kcal mol−1_1A_ HCP_, 104.6 kcal mol−1_1_− HCP_, 122.3 kcal mol−1_1A_ HPC_, and 171.6 kcal mol−1_1_− HPC_ at the cc-pVQZ EOM-CCSDT-3 level of theory. The physical properties of the 1A_ state with a predicted bond angle of 129.5° compare well with the experimentally reported first singlet state _A˜ 1A__. The excitation energy predicted for this excitation is T0=99.4 kcal mol−1_34 800 cm−1 , 4.31 eV_, in essentially perfect agreement with the experimental value of T0=99.3 kcal mol−1_34 746 cm−1 ,4.308 eV_. For the second lowest-lying excited singlet surface, 1_→1A_, four stationary points were found with Te values of 111.2 kcal mol−1 _21A_ HCP_, 112.4 kcal mol−1 _1_ HPC_, 125.6 kcal mol−1_2 1A_ HCP_, and 177.8 kcal mol−1_1_ HPC_. The predicted CP bond length and frequencies of the 2 1A_ state with a bond angle of 89.8° _1.707 Å, 666 and 979 cm−1_ compare reasonably well with those for the experimentally reported C ˜ 1A_ state _1.69 Å, 615 and 969 cm−1_. However, the excitation energy and bond angle do not agree well: theoretical values of 108.7 kcal mol−1 and 89.8° versus experimental values of 115.1 kcal mol−1 and 113°

Delayed maximum northern European summer temperatures during the Last Interglacial as a result of Greenland Ice Sheet melt

This is the author accepted manuscript. The final version is available from the Geological Society of America via the DOI in this record.Here we report a new quantitative mean July temperature reconstruction using non-biting midges (chironomids) from the Danish Last Interglacial (LIG) site Hollerup (spanning 127–116 ka). We find that peak mean July temperatures of 17.5 °C, similar to those of the present day (1961–1990 CE), were reached shortly before the onset of the regional Carpinus pollen zone. Through comparison to terrestrial and marine sequences we demonstrate that peak summer warmth took place some three millennia after the onset of LIG warming in Europe, a marked delay in line with records from the North Atlantic. Crucially, the warmest northern European summer temperatures appear to follow maximum Greenland Ice Sheet mass loss, implying that meltwater substantially reduced Atlantic Meridional Overturning Circulation and depressed European temperatures during the early part of the interglacial.Turney and Fogwill thank the Australian Research Council (grants FL100100195, FT120100004, LP120200724). Thanks to Bjørn Buchardt for providing the C:N data, Angela Self for help with statistical analysis, David Campbell and Alan Bedford for laboratory work, and three reviewers for their constructive comments

CSNL: A cost-sensitive non-linear decision tree algorithm

This article presents a new decision tree learning algorithm called CSNL that induces Cost-Sensitive Non-Linear decision trees. The algorithm is based on the hypothesis that nonlinear decision nodes provide a better basis than axis-parallel decision nodes and utilizes discriminant analysis to construct nonlinear decision trees that take account of costs of misclassification. The performance of the algorithm is evaluated by applying it to seventeen datasets and the results are compared with those obtained by two well known cost-sensitive algorithms, ICET and MetaCost, which generate multiple trees to obtain some of the best results to date. The results show that CSNL performs at least as well, if not better than these algorithms, in more than twelve of the datasets and is considerably faster. The use of bagging with CSNL further enhances its performance showing the significant benefits of using nonlinear decision nodes. The performance of the algorithm is evaluated by applying it to seventeen data sets and the results are compared with those obtained by two well known cost-sensitive algorithms, ICET and MetaCost, which generate multiple trees to obtain some of the best results to date. The results show that CSNL performs at least as well, if not better than these algorithms, in more than twelve of the data sets and is considerably faster. The use of bagging with CSNL further enhances its performance showing the significant benefits of using non-linear decision nodes

Incremental dimension reduction of tensors with random index

We present an incremental, scalable and efficient dimension reduction technique for tensors that is based on sparse random linear coding. Data is stored in a compactified representation with fixed size, which makes memory requirements low and predictable. Component encoding and decoding are performed on-line without computationally expensive re-analysis of the data set. The range of tensor indices can be extended dynamically without modifying the component representation. This idea originates from a mathematical model of semantic memory and a method known as random indexing in natural language processing. We generalize the random-indexing algorithm to tensors and present signal-to-noise-ratio simulations for representations of vectors and matrices. We present also a mathematical analysis of the approximate orthogonality of high-dimensional ternary vectors, which is a property that underpins this and other similar random-coding approaches to dimension reduction. To further demonstrate the properties of random indexing we present results of a synonym identification task. The method presented here has some similarities with random projection and Tucker decomposition, but it performs well at high dimensionality only (n>10^3). Random indexing is useful for a range of complex practical problems, e.g., in natural language processing, data mining, pattern recognition, event detection, graph searching and search engines. Prototype software is provided. It supports encoding and decoding of tensors of order >= 1 in a unified framework, i.e., vectors, matrices and higher order tensors.Comment: 36 pages, 9 figure

Rpgrip1 is required for rod outer segment development and ciliary protein trafficking in zebrafish

The authors would like to thank the Royal Society of London, the National Eye Research Centre, the Visual Research Trust, Fight for Sight, the W.H. Ross Foundation, the Rosetrees Trust, and the Glasgow Children’s Hospital Charity for supporting this work. This work was also supported by the Deanship of Scientific Research at King Saud University for funding this research (Research Project) grant number ‘RGP – VPP – 219’.Mutations in the RPGR-interacting protein 1 (RPGRIP1) gene cause recessive Leber congenital amaurosis (LCA), juvenile retinitis pigmentosa (RP) and cone-rod dystrophy. RPGRIP1 interacts with other retinal disease-causing proteins and has been proposed to have a role in ciliary protein transport; however, its function remains elusive. Here, we describe a new zebrafish model carrying a nonsense mutation in the rpgrip1 gene. Rpgrip1homozygous mutants do not form rod outer segments and display mislocalization of rhodopsin, suggesting a role for RPGRIP1 in rhodopsin-bearing vesicle trafficking. Furthermore, Rab8, the key regulator of rhodopsin ciliary trafficking, was mislocalized in photoreceptor cells of rpgrip1 mutants. The degeneration of rod cells is early onset, followed by the death of cone cells. These phenotypes are similar to that observed in LCA and juvenile RP patients. Our data indicate RPGRIP1 is necessary for rod outer segment development through regulating ciliary protein trafficking. The rpgrip1 mutant zebrafish may provide a platform for developing therapeutic treatments for RP patients.Publisher PDFPeer reviewe

Forward pi^0 Production and Associated Transverse Energy Flow in Deep-Inelastic Scattering at HERA

Deep-inelastic positron-proton interactions at low values of Bjorken-x down to x \approx 4.10^-5 which give rise to high transverse momentum pi^0 mesons are studied with the H1 experiment at HERA. The inclusive cross section for pi^0 mesons produced at small angles with respect to the proton remnant (the forward region) is presented as a function of the transverse momentum and energy of the pi^0 and of the four-momentum transfer Q^2 and Bjorken-x. Measurements are also presented of the transverse energy flow in events containing a forward pi^0 meson. Hadronic final state calculations based on QCD models implementing different parton evolution schemes are confronted with the data.Comment: 27 pages, 8 figures and 3 table

Simulation of dimensionality effects in thermal transport

The discovery of nanostructures and the development of growth and fabrication techniques of one- and two-dimensional materials provide the possibility to probe experimentally heat transport in low-dimensional systems. Nevertheless measuring the thermal conductivity of these systems is extremely challenging and subject to large uncertainties, thus hindering the chance for a direct comparison between experiments and statistical physics models. Atomistic simulations of realistic nanostructures provide the ideal bridge between abstract models and experiments. After briefly introducing the state of the art of heat transport measurement in nanostructures, and numerical techniques to simulate realistic systems at atomistic level, we review the contribution of lattice dynamics and molecular dynamics simulation to understanding nanoscale thermal transport in systems with reduced dimensionality. We focus on the effect of dimensionality in determining the phononic properties of carbon and semiconducting nanostructures, specifically considering the cases of carbon nanotubes, graphene and of silicon nanowires and ultra-thin membranes, underlying analogies and differences with abstract lattice models.Comment: 30 pages, 21 figures. Review paper, to appear in the Springer Lecture Notes in Physics volume "Thermal transport in low dimensions: from statistical physics to nanoscale heat transfer" (S. Lepri ed.

A comprehensive database of quality-rated fossil ages for Sahul’s Quaternary vertebrates

Published: 19 July 2016The study of palaeo-chronologies using fossil data provides evidence for past ecological and evolutionary processes, and is therefore useful for predicting patterns and impacts of future environmental change. However, the robustness of inferences made from fossil ages relies heavily on both the quantity and quality of available data. We compiled Quaternary non-human vertebrate fossil ages from Sahul published up to 2013. This, the FosSahul database, includes 9,302 fossil records from 363 deposits, for a total of 478 species within 215 genera, of which 27 are from extinct and extant megafaunal species (2,559 records). We also provide a rating of reliability of individual absolute age based on the dating protocols and association between the dated materials and the fossil remains. Our proposed rating system identified 2,422 records with high-quality ages (i.e., a reduction of 74%). There are many applications of the database, including disentangling the confounding influences of hypothetical extinction drivers, better spatial distribution estimates of species relative to palaeo-climates, and potentially identifying new areas for fossil discovery.Marta Rodríguez-Rey, y, Salvador Herrando-Pérez, Barry W. Brook, Frédérik Saltré, John Alroy, Nicholas Beeton, Michael I. Bird, Alan Cooper, Richard Gillespie, Zenobia Jacobs, Christopher N. Johnson, Gifford H. Miller, Gavin J. Prideaux, Richard G. Roberts, Chris S.M. Turney and Corey J.A. Bradsha

Antarctic ice sheet discharge driven by atmosphere-ocean feedbacks at the Last Glacial Termination

Reconstructing the dynamic response of the Antarctic ice sheets to warming during the Last Glacial Termination (LGT; 18,000–11,650 yrs ago) allows us to disentangle ice-climate feedbacks that are key to improving future projections. Whilst the sequence of events during this period is reasonably well-known, relatively poor chronological control has precluded precise alignment of ice, atmospheric and marine records, making it difficult to assess relationships between Antarctic ice-sheet (AIS) dynamics, climate change and sea level. Here we present results from a highly-resolved ‘horizontal ice core’ from the Weddell Sea Embayment, which records millennial-scale AIS dynamics across this extensive region. Counterintuitively, we find AIS mass-loss across the full duration of the Antarctic Cold Reversal (ACR; 14,600–12,700 yrs ago), with stabilisation during the subsequent millennia of atmospheric warming. Earth-system and ice-sheet modelling suggests these contrasting trends were likely Antarctic-wide, sustained by feedbacks amplified by the delivery of Circumpolar Deep Water onto the continental shelf. Given the anti-phase relationship between inter-hemispheric climate trends across the LGT our findings demonstrate that Southern Ocean-AIS feedbacks were controlled by global atmospheric teleconnections. With increasing stratification of the Southern Ocean and intensification of mid-latitude westerly winds today, such teleconnections could amplify AIS mass loss and accelerate global sea-level rise