Influence of Triplet Instabilities in TDDFT Peach, Michael J. G; Williamson, Matthew J; Tozer, David J
Journal of chemical theory and computation,
11/2011, Letnik:
7, Številka:
11
Journal Article
Recenzirano
Odprti dostop
Singlet and triplet vertical excitation energies from time-dependent density functional theory (TDDFT) can be affected in different ways by the inclusion of exact exchange in hybrid or ...Coulomb-attenuated/range-separated exchange–correlation functionals; in particular, triplet excitation energies can become significantly too low. To investigate these issues, the explicit dependence of excitation energies on exact exchange is quantified for four representative molecules, paying attention to the effect of constant, short-range, and long-range contributions. A stability analysis is used to verify that the problematic TDDFT triplet excitations can be understood in terms of the ground state triplet instability problem, and it is proposed that a Hartree–Fock stability analysis should be used to identify triplet excitations for which the presence of exact exchange in the TDDFT functional is undesirable. The use of the Tamm–Dancoff approximation (TDA) significantly improves the problematic triplet excitation energies, recovering the correct state ordering in benzoquinone; it also affects the corresponding singlet states, recovering the correct state ordering in naphthalene. The impressive performance of the TDA is maintained for a wide range of molecules across representative functionals.
Summary
Background
Fibrotic stricture is a common complication of Crohn's disease (CD) affecting approximately half of all patients. No specific anti‐fibrotic therapies are available; however, ...several therapies are currently under evaluation. Drug development for the indication of stricturing CD is hampered by a lack of standardised definitions, diagnostic modalities, clinical trial eligibility criteria, endpoints and treatment targets in stricturing CD.
Aim
To standardise definitions, diagnosis and treatment targets for anti‐fibrotic stricture therapies in Chron's disease.
Methods
An interdisciplinary expert panel consisting of 15 gastroenterologists and radiologists was assembled. Using modified RAND/University of California Los Angeles appropriateness methodology, 109 candidate items derived from systematic review and expert opinion focusing on small intestinal strictures were anonymously rated as inappropriate, uncertain or appropriate. Survey results were discussed as a group before a second and third round of voting.
Results
Fibrotic strictures are defined by the combination of luminal narrowing, wall thickening and pre‐stenotic dilation. Definitions of anastomotic (at site of prior intestinal resection with anastomosis) and naïve small bowel strictures were similar; however, there was uncertainty regarding wall thickness in anastomotic strictures. Magnetic resonance imaging is considered the optimal technique to define fibrotic strictures and assess response to therapy. Symptomatic strictures are defined by abdominal distension, cramping, dietary restrictions, nausea, vomiting, abdominal pain and post‐prandial abdominal pain. Need for intervention (endoscopic balloon dilation or surgery) within 24‐48 weeks is considered the appropriate endpoint in pharmacological trials.
Conclusions
Consensus criteria for diagnosis and response to therapy in stricturing Crohn's disease should inform both clinical practice and trial design.
Gravitational waves enable tests of general relativity in the highly dynamical and strong-field regime. Using events detected by LIGO-Virgo up to 1 October 2019, we evaluate the consistency of the ...data with predictions from the theory. We first establish that residuals from the best-fit waveform are consistent with detector noise, and that the low- and high-frequency parts of the signals are in agreement. We then consider parametrized modifications to the waveform by varying post-Newtonian and phenomenological coefficients, improving past constraints by factors of ∼2; we also find consistency with Kerr black holes when we specifically target signatures of the spin-induced quadrupole moment. Looking for gravitational-wave dispersion, we tighten constraints on Lorentz-violating coefficients by a factor of ∼2.6 and bound the mass of the graviton to m(g)≤1.76 x 10^(-23) eV/sq. c with 90% credibility. We also analyze the properties of the merger remnants by measuring ringdown frequencies and damping times, constraining fractional deviations away from the Kerr frequency to δ{\hat {f}}(220)=0.03(+0.38,-0.35) for the fundamental quadrupolar mode, and δ{\hat {f}}(221)=0.04(+0.27,-0.32) for the first overtone; additionally, we find no evidence for postmerger echoes. Finally, we determine that our data are consistent with tensorial polarizations through a template-independent method. When possible, we assess the validity of general relativity based on collections of events analyzed jointly. We find no evidence for new physics beyond general relativity, for black hole mimickers, or for any unaccounted systematics.
A number of scales are used to estimate the severity of depression. However, differences between self-report and clinician rating, multi-dimensionality and different weighting of individual symptoms ...in summed scores may affect the validity of measurement. In this study we examined and integrated the psychometric properties of three commonly used rating scales.
The 17-item Hamilton Depression Rating Scale (HAMD-17), the Montgomery-Asberg Depression Rating Scale (MADRS) and the Beck Depression Inventory (BDI) were administered to 660 adult patients with unipolar depression in a multi-centre pharmacogenetic study. Item response theory (IRT) and factor analysis were used to evaluate their psychometric properties and estimate true depression severity, as well as to group items and derive factor scores.
The MADRS and the BDI provide internally consistent but mutually distinct estimates of depression severity. The HAMD-17 is not internally consistent and contains several items less suitable for out-patients. Factor analyses indicated a dominant depression factor. A model comprising three dimensions, namely 'observed mood and anxiety', 'cognitive' and 'neurovegetative', provided a more detailed description of depression severity.
The MADRS and the BDI can be recommended as complementary measures of depression severity. The three factor scores are proposed for external validation.
Tree species exceeding 70 m in height are rare globally. Giant gymnosperms are concentrated near the Pacific coast of the USA, while the tallest angiosperms are eucalypts (Eucalyptus spp.) in ...southern and eastern Australia. Giant eucalypts co-occur with rain-forest trees in eastern Australia, creating unique vegetation communities comprising fire-dependent trees above fire-intolerant rain-forest. However, giant eucalypts can also tower over shrubby understoreys (e.g. in Western Australia). The local abundance of giant eucalypts is controlled by interactions between fire activity and landscape setting. Giant eucalypts have features that increase flammability (e.g. oil-rich foliage and open crowns) relative to other rain-forest trees but it is debatable if these features are adaptations. Probable drivers of eucalypt gigantism are intense intra-specific competition following severe fires, and inter-specific competition among adult trees. However, we suggest that this was made possible by a general capacity of eucalypts for ‘hyper-emergence’. We argue that, because giant eucalypts occur in rain-forest climates and share traits with rain-forest pioneers, they should be regarded as long-lived rain-forest pioneers, albeit with a particular dependence on fire for regeneration. These unique ecosystems are of high conservation value, following substantial clearing and logging over 150 yr.
Prescribed burning is used to reduce the occurrence, extent and severity of uncontrolled fires in many flammable landscapes. However, epidemiologic evidence of the human health impacts of landscape ...fire smoke emissions is shaping fire management practice through increasingly stringent environmental regulation and public health policy. An unresolved question, critical for sustainable fire management, concerns the comparative human health effects of smoke from wild and prescribed fires. Here we review current knowledge of the health effects of landscape fire emissions and consider the similarities and differences in smoke from wild and prescribed fires with respect to the typical combustion conditions and fuel properties, the quality and magnitude of air pollution emissions, and the potential for dispersion to large populations. We further examine the interactions between these considerations, and how they may shape the longer term smoke regimes to which populations are exposed. We identify numerous knowledge gaps and propose a conceptual framework that describes pathways to better understanding of the health trade-offs of prescribed and wildfire smoke regimes.
Campylobacter hepaticus, the causative agent of Spotty Liver Disease (SLD) is an important disease in cage-free egg producing chickens causing mortality and production drops. C. hepaticus is a slow ...growing Campylobacter easily overgrown by fecal bacteria. It is currently only reliably isolatable from bile samples. A selective media for isolation from feces or environment would assist diagnosis and impact assessment. Growth of five Australian C. hepaticus isolates was studied using Horse blood agar (HBA), sheep blood agar (SBA), Bolton, Preston and Brain Heart Infusion (BHI) base media. Blood and/or bile were added to Bolton, Preston and BHI medias. C. jejuni was used as a positive control. Plates were incubated in duplicate under microaerophilic conditions at 42°C for 10 days and examined at days 3-5 and 7-10 of incubation. Each isolate was examined for sensitivity to 14 antimicrobials using HBA sensitivity plates. Growth was inhibited by BHI and by added bile, while blood improved growth. Further replicates using SBA, HBA, Bolton and Preston media showed best growth on Bolton agar with blood. All five C. hepaticus isolates were resistant to trimethoprim and vancomycin, while four were also resistant to rifampicin and bacitracin. Media based upon Bolton plus blood supplemented with vancomycin and trimethoprim might be used as the most appropriate media for selective growth of C. hepaticus. The addition of bile to media for C. hepaticus isolation and growth will inhibit growth and is not advised.
A challenge in obstetrics is to distinguish pathological symptoms from those associated with normal changes of pregnancy, typified by the need to differentiate whether gestational pruritus of the ...skin is an early symptom of intrahepatic cholestasis of pregnancy (ICP) or due to benign pruritus gravidarum. ICP is characterized by raised serum bile acids and complicated by spontaneous preterm labor and stillbirth. A biomarker for ICP would be invaluable for early diagnosis and treatment and to enable its differentiation from other maternal diseases. Three progesterone sulfate compounds, whose concentrations have not previously been studied, were newly synthesized and assayed in the serum of three groups of ICP patients and found to be significantly higher in ICP at 9‐15 weeks of gestation and prior to symptom onset (group 1 cases/samples: ICP n = 35/80, uncomplicated pregnancy = 29/100), demonstrating that all three progesterone sulfates are prognostic for ICP. Concentrations of progesterone sulfates were associated with itch severity and, in combination with autotaxin, distinguished pregnant women with itch that would subsequently develop ICP from pruritus gravidarum (group 2: ICP n = 41, pruritus gravidarum n = 14). In a third group of first‐trimester samples all progesterone sulfates were significantly elevated in serum from low‐risk asymptomatic women who subsequently developed ICP (ICP/uncomplicated pregnancy n = 54/51). Finally, we show mechanistically that progesterone sulfates mediate itch by evoking a Tgr5‐dependent scratch response in mice. Conclusion: Our discovery that sulfated progesterone metabolites are a prognostic indicator for ICP will help predict onset of ICP and distinguish it from benign pruritus gravidarum, enabling targeted obstetric care to a high‐risk population. Delineation of a progesterone sulfate‐TGR5 pruritus axis identifies a therapeutic target for itch management in ICP. (Hepatology 2016;63:1287–1298)
Quenching and partitioning (Q&P) produces steel microstructures with martensite and austenite that exhibit promising property combinations for third generation advanced high strength steels. ...Understanding the kinetics of reactions that compete for available carbon, such as carbide formation, is critical for alloying and processing design and achieving austenite enrichment and retention during Q&P. Mössbauer effect spectroscopy (MES) was used to characterize Q&P microstructures in a 0.38C–1.54Mn–1.48Siwt.% steel after quenching to 225°C and partitioning at 400°C for 10 or 300s, with an emphasis on transition carbides. The recoilless fraction for η-carbide was calculated and a correction for saturation of the MES absorption spectrum was applied, making quantitative measurements of small amounts of η-carbide, including non-stoichiometric η-carbide, possible in Q&P microstructures. Complementary transmission electron microscopy confirmed the presence of η-carbides, and MES and X-ray diffraction were used to characterize the austenite. The amount of η-carbide formed during Q&P ranged from 1.4 to 2.4at.%, accounting for a substantial portion (∼24% to 41%) of the bulk carbon content of the steel. The amount (5.0at.%) of η-carbide that formed after quenching and tempering (Q&T) at 400°C for 300s was significantly greater than after partitioning at 400°C for 300s (2.4at.%), suggesting that carbon partitioning from martensite to austenite occurs in conjunction with η-carbide formation during Q&P in these specimens.
The second Gravitational-Wave Transient Catalog, GWTC-2, reported on 39 compact binary coalescences observed by the Advanced LIGO and Advanced Virgo detectors between 1 April 2019 15∶00 UTC and 1 ...October 2019 15∶00 UTC. Here, we present GWTC-2.1, which reports on a deeper list of candidate events observed over the same period. We analyze the final version of the strain data over this period with improved calibration and better subtraction of excess noise, which has been publicly released. We employ three matched-filter search pipelines for candidate identification, and estimate the probability of astrophysical origin for each candidate event. While GWTC-2 used a false alarm rate threshold of 2 per year, we include in GWTC-2.1, 1201 candidates that pass a false alarm rate threshold of 2 per day. We calculate the source properties of a subset of 44 high-significance candidates that have a probability of astrophysical origin greater than 0.5. Of these candidates, 36 have been reported in GWTC-2. We also calculate updated source properties for all binary black hole events previously reported in GWTC-1. If the eight additional high-significance candidates presented here are astrophysical, the mass range of events that are unambiguously identified as binary black holes (both objects ≥3M⊙) is increased compared to GWTC-2, with total masses from ∼14M⊙ for GW190924_021846 to ∼182M⊙ for GW190426_190642. Source properties calculated using our default prior suggest that the primary components of two new candidate events (GW190403_051519 and GW190426_190642) fall in the mass gap predicted by pair-instability supernova theory. We also expand the population of binaries with significantly asymmetric mass ratios reported in GWTC-2 by an additional two events (the mass ratio is less than 0.65 and 0.44 at 90% probability for GW190403_051519 and GW190917_114630 respectively), and find that two of the eight new events have effective inspiral spins χeff>0 (at 90% credibility), while no binary is consistent with χeff<0 at the same significance. We provide updated estimates for rates of binary black hole and binary neutron star coalescence in the local Universe.
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