The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

We report rate coefficients for the relaxation of OH(v = 1) and OD(v = 1) by H2O and D2O as a function of temperature between 251 and 390 K. All four rate coefficients exhibit a negative dependence on temperature. In Arrhenius form, the rate coefficients for relaxation (in units of 10–12 cm3 molecule–1 s–1) can be expressed as: for OH(v = 1) + H2O between 263 and 390 K: k = (2.4 ± 0.9) exp((460 ± 115)/T); for OH(v = 1) + D2O between 256 and 371 K: k = (0.49 ± 0.16) exp((610 ± 90)/T); for OD(v = 1) + H2O between 251 and 371 K: k = (0.92 ± 0.16) exp((485 ± 48)/T); for OD(v = 1) + D2O between 253 and 366 K: k = (2.57 ± 0.09) exp((342 ± 10)/T). Rate coefficients at (297 ± 1 K) are also reported for the relaxation of OH(v = 2) by D2O and the relaxation of OD(v = 2) by H2O and D2O. The results are discussed in terms of a mechanism involving the formation of hydrogen-bonded complexes in which intramolecular vibrational energy redistribution can occur at rates competitive with re-dissociation to the initial collision partners in their original vibrational states. New ab initio calculations on the H2O–HO system have been performed which, inter alia, yield vibrational frequencies for all four complexes: H2O–HO, D2O–HO, H2O–DO and D2O–DO. These data are then employed, adapting a formalism due to Troe (J. Troe, J. Chem. Phys., 1977, 66, 4758), in order to estimate the rates of intramolecular energy transfer from the OH (OD) vibration to other modes in the complexes in order to explain the measured relaxation rates—assuming that relaxation proceeds via the hydrogen-bonded complexes

Effective patient–clinician interaction to improve treatment outcomes for patients with psychosis: a mixed-methods design

BACKGROUND:At least 100,000 patients with schizophrenia receive care from community mental health teams (CMHTs) in England. These patients have regular meetings with clinicians, who assess them, engage them in treatment and co-ordinate care. As these routine meetings are not commonly guided by research evidence, a new intervention, DIALOG, was previously designed to structure consultations. Using a hand-held computer, clinicians asked patients to rate their satisfaction with eight life domains and three treatment aspects, and to indicate whether or not additional help was needed in each area, with responses being graphically displayed and compared with previous ratings. In a European multicentre trial, the intervention improved patients’ quality of life over a 1-year period. The current programme builds on this research by further developing DIALOG in the UK. RESEARCH QUESTIONS:(1) How can the practical procedure of the intervention be improved, including the software used and the design of the user interface? (2) How can elements of resource-oriented interventions be incorporated into a clinician manual and training programme for a new, more extensive ‘DIALOG+’ intervention? (3) How effective and cost-effective is the new DIALOG+ intervention in improving treatment outcomes for patients with schizophrenia or a related disorder? (4) What are the views of patients and clinicians regarding the new DIALOG+ intervention? METHODS:We produced new software on a tablet computer for CMHTs in the NHS, informed by analysis of videos of DIALOG sessions from the original trial and six focus groups with 18 patients with psychosis. We developed the new ‘DIALOG+’ intervention in consultation with experts, incorporating principles of solution-focused therapy when responding to patients’ ratings and specifying the procedure in a manual and training programme for clinicians. We conducted an exploratory cluster randomised controlled trial with 49 clinicians and 179 patients with psychosis in East London NHS Foundation Trust, comparing DIALOG+ with an active control. Clinicians working as care co-ordinators in CMHTs (along with their patients) were cluster randomised 1 : 1 to either DIALOG+ or treatment as usual plus an active control, to prevent contamination. Intervention and control were to be administered monthly for 6 months, with data collected at baseline and at 3, 6 and 12 months following randomisation. The primary outcome was subjective quality of life as measured on the Manchester Short Assessment of Quality of Life; secondary outcomes were also measured. We also established the cost-effectiveness of the DIALOG intervention using data from the Client Service Receipt Inventory, which records patients’ retrospective reports of using health- and social-care services, including hospital services, outpatient services and medication, in the 3 months prior to each time point. Data were supplemented by the clinical notes in patients’ medical records to improve accuracy. We conducted an exploratory thematic analysis of 16 video-recorded DIALOG+ sessions and measured adherence in these videos using a specially developed adherence scale. We conducted focus groups with patients (n = 19) and clinicians (n = 19) about their experiences of the intervention, and conducted thematic analyses. We disseminated the findings and made the application (app), manual and training freely available, as well as producing a protocol for a definitive trial. RESULTS:Patients receiving the new intervention showed more favourable quality of life in the DIALOG+ group after 3 months (effect size: Cohen’s d = 0.34), after 6 months (Cohen’s d = 0.29) and after 12 months (Cohen’s d = 0.34). An analysis of video-recorded DIALOG+ sessions showed inconsistent implementation, with adherence to the intervention being a little over half of the possible score. Patients and clinicians from the DIALOG+ arm of the trial reported many positive experiences with the intervention, including better self-expression and improved efficiency of meetings. Difficulties reported with the intervention were addressed by further refining the DIALOG+ manual and training. Cost-effectiveness analyses found a 72% likelihood that the intervention both improved outcomes and saved costs. LIMITATIONS:The research was conducted solely in urban east London, meaning that the results may not be broadly generalisable to other settings. CONCLUSIONS:(1) Although services might consider adopting DIALOG+ based on the existing evidence, a definitive trial appears warranted; (2) applying DIALOG+ to patient groups with other mental disorders may be considered, and to groups with physical health problems; (3) a more flexible use with variable intervals might help to make the intervention even more acceptable and effective; (4) more process evaluation is required to identify what mechanisms precisely are involved in the improvements seen in the intervention group in the trial; and (5) what appears to make DIALOG+ effective is that it is not a separate treatment and not a technology that is administered by a specialist; rather, it changes and utilises the existing therapeutic relationship between patients and clinicians in CMHTs to initiate positive change, helping the patients to improve their quality of life. FUTURE RESEARCH:Future studies should include a definitive trial on DIALOG+ and test the effectiveness of the intervention with other populations, such as people with depression. TRIAL REGISTRATION:Current Controlled Trials ISRCTN34757603. FUNDING:The National Institute for Health Research Programme Grants for Applied Research programme

Biomass burning and urban air pollution over the Central Mexican Plateau

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow

Deriving genetic programming fitness properties by static analysis

Deriving Genetic Programming Fitness Properties by Static Analysis Colin G. Johnson The aim of this paper is to introduce the idea of using static analysis of computer programs as a way of measuring fitness in genetic programming. Such techniques extract information about the programs without explicitly running them, and in particular they infer properties which hold across the whole of the input space of a program. This can be applied to measure fitness, and has a number of advantages over measuring fitness by running members of the population on test cases. The most important advantage is that if a solution is found then it is possible to formally trust that solution to be correct across all inputs. This paper introduces these ideas, discusses various ways in which they could be applied, discusses the type of problems for which they are appropriate, and ends by giving a simple test example and some questions for future research

Practical long-distance quantum key distribution system using decoy levels

Quantum key distribution (QKD) has the potential for widespread real-world applications. To date no secure long-distance experiment has demonstrated the truly practical operation needed to move QKD from the laboratory to the real world due largely to limitations in synchronization and poor detector performance. Here we report results obtained using a fully automated, robust QKD system based on the Bennett Brassard 1984 protocol (BB84) with low-noise superconducting nanowire single-photon detectors (SNSPDs) and decoy levels. Secret key is produced with unconditional security over a record 144.3 km of optical fibre, an increase of more than a factor of five compared to the previous record for unconditionally secure key generation in a practical QKD system.Comment: 9 page

Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air

Stable water isotope and surface heat flux simulation using ISOLSM: Evaluation against in-situ measurements

Author's manuscript made available in accordance with the publisher's policy.The stable isotopes of water are useful tracers of water sources and hydrological processes. Stable water isotope-enabled land surface modeling is a relatively new approach for characterizing the hydrological cycle, providing spatial and temporal variability for a number of hydrological processes. At the land surface, the integration of stable water isotopes with other meteorological measurements can assist in constraining surface heat flux estimates and discriminate between evaporation (E) and transpiration (T). However, research in this area has traditionally been limited by a lack of continuous in-situ isotopic observations. Here, the National Centre for Atmospheric Research stable isotope-enabled Land Surface Model (ISOLSM) is used to simulate the water and energy fluxes and stable water isotope variations. The model was run for a period of one month with meteorological data collected from a coastal sub-tropical site near Sydney, Australia. The modeled energy fluxes (latent heat and sensible heat) agreed reasonably well with eddy covariance observations, indicating that ISOLSM has the capacity to reproduce observed flux behavior. Comparison of modeled isotopic compositions of evapotranspiration (ET) against in-situ Fourier Transform Infrared spectroscopy (FTIR) measured bulk water vapor isotopic data (10 m above the ground), however, showed differences in magnitude and temporal patterns. The disparity is due to a small contribution from local ET fluxes to atmospheric boundary layer water vapor (∼1% based on calculations using ideal gas law) relative to that advected from the ocean for this particular site. Using ISOLSM simulation, the ET was partitioned into E and T with 70% being T. We also identified that soil water from different soil layers affected T and E differently based on the simulated soil isotopic patterns, which reflects the internal working of ISOLSM. These results highlighted the capacity of using the isotope-enabled models to discriminate between different hydrological components and add insight into expected hydrological behavior

Improved Nearside-Farside Decomposition of Elastic Scattering Amplitudes

A simple technique is described, that provides improved nearside-farside (NF) decompositions of elastic scattering amplitudes. The technique, involving the resummation of a Legendre partial wave series, reduces the importance of unphysical contributions to NF subamplitudes, which can arise in more conventional NF decompositions. Applications are made to a strong absorption model and to a $^{16}$O + $^{12}$C optical potential at $E_{\text{lab}} = 132$ MeV.Comment: 5 pages, 2 figure

What makes for prize-winning television?

We investigate the determinants of success in four international television awards festivals between 1994 and 2012. We find that countries with larger markets and greater expenditure on public broadcasting tend to win more awards, but that the degree of concentration in the market for television and rates of penetration of pay-per-view television are unrelated to success. These findings are consistent with general industrial organisation literature on quality and market size, and with media policy literature on public service broadcasting acting as a force for quality. However, we also find that ‘home countries’ enjoy a strong advantage in these festivals, which is not consistent with festival success acting as a pure proxy for television quality

Dryland ecohydrology and climate change: critical issues and technical advances

Drylands cover about 40% of the terrestrial land surface and account for approximately 40% of global net primary productivity. Water is fundamental to the biophysical processes that sustain ecosystem function and food production, particularly in drylands where a tight coupling exists between ecosystem productivity, surface energy balance, biogeochemical cycles, and water resource availability. Currently, drylands support at least 2 billion people and comprise both natural and managed ecosystems. In this synthesis, we identify some current critical issues in the understanding of dryland systems and discuss how arid and semiarid environments are responding to the changes in climate and land use. The issues range from societal aspects such as rapid population growth, the resulting food and water security, and development issues, to natural aspects such as ecohydrological consequences of bush encroachment and the causes of desertification. To improve current understanding and inform upon the needed research efforts to address these critical issues, we identify some recent technical advances in terms of monitoring dryland water dynamics, water budget and vegetation water use, with a focus on the use of stable isotopes and remote sensing. These technological advances provide new tools that assist in addressing critical issues in dryland ecohydrology under climate change