Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the Restricted Active Space Self-Consistent Field method including spin-orbit coupling is used to cope with this challenge and to calculate valence and core photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the $\text{[Fe(H}_2\text{O)}_6\text{]}^{2+}$ complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments

Quality Improvement in Pediatric Head Trauma with PECARN Rules Implementation as Computerized Decision Support

Background: For the 1.4 million emergency department (ED) visits for traumatic brain injury (TBI) annually in the United States, computed tomography (CT) may be over utilized. The Pediatric Emergency Care Applied Research Network developed 2 prediction rules to identify children at very low risk of clinically important TBI. We implemented these prediction rules as decision support within our electronic health record (EHR) to reduce CT. Objective: To test EHR decision support implementation in reducing CT rates for head trauma at 2 pediatric EDs. Methods: We compared monthly CT rates 1 year before [preimplementation (PRE)] and 1 year after [postimplementation (POST)] decision support implementation. The primary outcome was change in CT use rate over time, measured using statistical process control charts. Secondary analyses included multivariate comparisons of PRE to POST. Balancing measures included ED length of stay and returns within 7 days after ED release. Results: There were 2,878 patients with head trauma (1,329 PRE and 1,549 POST) included. Statistical process control charts confirmed decreased CT rates over time POST that was not present PRE. Secondary statistical analyses confirmed that CT scan utilization rates decreased from 26.8% to 18.9% (unadjusted Odds Ratio [OR], 0.64; 95% Confidence Interval [CI], 0.53 -0.76; adjusted OR, 0.71; 95% CI, 0.58 -0.86). Length of stay was unchanged. There was no increase in returns within 7 days and no significant missed diagnoses. Conclusions: Implementation of EHR-integrated decision support for children with head trauma presenting to the ED is associated with a decrease in CT utilization and no increase in significant safety events

Techniques and resources for storm-scale numerical weather prediction

The topics discussed include the following: multiscale application of the 5th-generation PSU/NCAR mesoscale model, the coupling of nonhydrostatic atmospheric and hydrostatic ocean models for air-sea interaction studies; a numerical simulation of cloud formation over complex topography; adaptive grid simulations of convection; an unstructured grid, nonhydrostatic meso/cloud scale model; efficient mesoscale modeling for multiple scales using variable resolution; initialization of cloud-scale models with Doppler radar data; and making effective use of future computing architectures, networks, and visualization software

Fluorescent analogues of Human α-Calcitonin Gene-Related Peptide with vasodilator potency

Human α-calcitonin gene-related peptide (h-α-CGRP) is a highly potent vasodilator peptide that belongs to the family of calcitonin peptides. There are two forms of CGRP receptors in humans and rodents: α-CGRP receptor predominately found in the cardiovascular system and β-CGRP receptor predominating in the gastrointestinal tract. The CGRP receptors are primarily localized to C and Aδ sensory fibers, where they are involved in nociceptive transmission and migraine pathophysiology. These fibers are found both peripherally and centrally, with extensive perivascular location. The CGRP receptors belong to the class B G-protein-coupled receptors, and they are primarily associated to signaling via Gα proteins. The objectives of the present work were: (i) synthesis of three single-labelled fluorescent analogues of h-α-CGRP by 9-fluorenylmethyloxycarbonyl (Fmoc)-based solid-phase peptide synthesis, and (ii) testing of their biological activity in isolated human, mouse, and rat arteries by using a small-vessel myograph setup. The three analogues were labelled with 5(6)-carboxyfluorescein via the spacer 6-aminohexanoic acid at the chain of Lys24 or Lys35. Circular dichroism (CD) experiments were performed to obtain information on the secondary structure of these fluorescently labelled peptides. The CD spectra indicated that the folding of all three analogues was similar to that of native α-CGRP. The three fluorescent analogues of α-CGRP were successfully prepared with a purity of >95%. In comparison to α-CGRP, the three analogues exhibited similar efficacy, but different potency in producing a vasodilator effect. The analogue labelled at the N-terminus proved to be the most readily synthesized, but it was found to possess the lowest vasodilator potency. The analogues labelled at Lys35 or Lys24 exhibited an acceptable reduction in potency (i.e., 3–5 times and 5–10 times less potent, respectively), and thus they have potential for use in further investigations of receptor internalization and neuronal reuptake

First radial velocity results from the MINiature Exoplanet Radial Velocity Array (MINERVA)

The MINiature Exoplanet Radial Velocity Array (MINERVA) is a dedicated observatory of four 0.7m robotic telescopes fiber-fed to a KiwiSpec spectrograph. The MINERVA mission is to discover super-Earths in the habitable zones of nearby stars. This can be accomplished with MINERVA's unique combination of high precision and high cadence over long time periods. In this work, we detail changes to the MINERVA facility that have occurred since our previous paper. We then describe MINERVA's robotic control software, the process by which we perform 1D spectral extraction, and our forward modeling Doppler pipeline. In the process of improving our forward modeling procedure, we found that our spectrograph's intrinsic instrumental profile is stable for at least nine months. Because of that, we characterized our instrumental profile with a time-independent, cubic spline function based on the profile in the cross dispersion direction, with which we achieved a radial velocity precision similar to using a conventional "sum-of-Gaussians" instrumental profile: 1.8 m s$^{-1}$ over 1.5 months on the RV standard star HD 122064. Therefore, we conclude that the instrumental profile need not be perfectly accurate as long as it is stable. In addition, we observed 51 Peg and our results are consistent with the literature, confirming our spectrograph and Doppler pipeline are producing accurate and precise radial velocities.Comment: 22 pages, 9 figures, submitted to PASP, Peer-Reviewed and Accepte

Evolutionary History of the HAP2/GCS1 Gene and Sexual Reproduction in Metazoans

The HAP2/GCS1 gene first appeared in the common ancestor of plants, animals, and protists, and is required in the male gamete for fusion to the female gamete in the unicellular organisms Chlamydomonas and Plasmodium. We have identified a HAP2/GCS1 gene in the genome sequence of the sponge Amphimedon queenslandica. This finding provides a continuous evolutionary history of HAP2/GCS1 from unicellular organisms into the metazoan lineage. Divergent versions of the HAP2/GCS1 gene are also present in the genomes of some but not all arthropods. By examining the expression of the HAP2/GCS1 gene in the cnidarian Hydra, we have found the first evidence supporting the hypothesis that HAP2/GCS1 was used for male gamete fusion in the ancestor of extant metazoans and that it retains that function in modern cnidarians

Revealing important nocturnal and day-to-day variations in fire smoke emissions through a multiplatform inversion

We couple airborne, ground-based, and satellite observations; conduct regional simulations; and develop and apply an inversion technique to constrain hourly smoke emissions from the Rim Fire, the third largest observed in California, USA. Emissions constrainedwithmultiplatform data show notable nocturnal enhancements (sometimes over a factor of 20), correlate better with daily burned area data, and are a factor of 2–4 higher than a priori estimates, highlighting the need for improved characterization of diurnal profiles and day-to-day variability when modeling extreme fires. Constraining only with satellite data results in smaller enhancements mainly due to missing retrievals near the emissions source, suggesting that top-down emission estimates for these events could be underestimated and a multi-platform approach is required to resolve them. Predictions driven by emissions constrained with multi-platform data present significant variations in downwind air quality and in aerosol feedback on meteorology, emphasizing the need for improved emissions estimates during exceptional events

Air Quality Modeling for the Urban Jackson, Mississippi Region Using a High Resolution WRF/Chem Model

In this study, an attempt was made to simulate the air quality with reference to ozone over the Jackson (Mississippi) region using an online WRF/Chem (Weather Research and Forecasting–Chemistry) model. The WRF/Chem model has the advantages of the integration of the meteorological and chemistry modules with the same computational grid and same physical parameterizations and includes the feedback between the atmospheric chemistry and physical processes. The model was designed to have three nested domains with the inner-most domain covering the study region with a resolution of 1 km. The model was integrated for 48 hours continuously starting from 0000 UTC of 6 June 2006 and the evolution of surface ozone and other precursor pollutants were analyzed. The model simulated atmospheric flow fields and distributions of NO2 and O3 were evaluated for each of the three different time periods. The GIS based spatial distribution maps for ozone, its precursors NO, NO2, CO and HONO and the back trajectories indicate that all the mobile sources in Jackson, Ridgeland and Madison contributing significantly for their formation. The present study demonstrates the applicability of WRF/Chem model to generate quantitative information at high spatial and temporal resolution for the development of decision support systems for air quality regulatory agencies and health administrators

A framework for convection and boundary layer parameterization derived from conditional filtering

A new theoretical framework is derived for parameterization of subgrid physical processes in atmospheric models; the application to parameterization of convection and boundary layer fluxes is a particular focus. The derivation is based on conditional filtering, which uses a set of quasi-Lagrangian labels to pick out different regions of the fluid, such as convective updrafts and environment, before applying a spatial filter. This results in a set of coupled prognostic equations for the different fluid components, including subfilter-scale flux terms and entrainment/detrainment terms. The framework can accommodate different types of approaches to parameterization, such as local turbulence approaches and mass-flux approaches. It provides a natural way to distinguish between local and nonlocal transport processes, and makes a clearer conceptual link to schemes based on coherent structures such as convective plumes or thermals than the straightforward application of a filter without the quasi-Lagrangian labels. The framework should facilitate the unification of different approaches to parameterization by highlighting the different approximations made, and by helping to ensure that budgets of energy, entropy, and momentum are handled consistently and without double counting. The framework also points to various ways in which traditional parameterizations might be extended, for example by including additional prognostic variables. One possibility is to allow the large-scale dynamics of all the fluid components to be handled by the dynamical core. This has the potential to improve several aspects of convection-dynamics coupling, such as dynamical memory, the location of compensating subsidence, and the propagation of convection to neighboring grid columns