ABSTRACT
We report a joint experimental and theoretical study of the low-pressure phase of α'-Ga2S3 under compression. Theoretical ab initio calculations have been compared to X-ray diffraction and Raman scattering measurements under high pressure carried out up to 17.5 and 16.1 GPa, respectively. In addition, we report Raman scattering measurements of α'-Ga2S3 at high temperature that have allowed us to study its anharmonic properties. To understand better the compression of this compound, we have evaluated the topological properties of the electron density, the electron localization function, and the electronic properties as a function of pressure. As a result, we shed light on the role of the Ga-S bonds, the van der Waals interactions inside the channels of the crystalline structure, and the single and double lone electron pairs of the sulphur atoms in the anisotropic compression of α'-Ga2S3. We found that the structural channels are responsible for the anisotropic properties of α'-Ga2S3 and the A'(6) phonon, known as the breathing mode and associated with these channels, exhibits the highest anharmonic behaviour. Finally, we report calculations of the electronic band structure of α'-Ga2S3 at different pressures and find a nonlinear pressure behaviour of the direct band gap and a pressure-induced direct-to-indirect band gap crossover that is similar to the behaviour previously reported in other ordered-vacancy compounds, including ß-Ga2Se3. The importance of the single and, more specially, the double lone electron pairs of sulphur in the pressure dependence of the topmost valence band of α'-Ga2S3 is stressed.
ABSTRACT
AIM: The main goal of this study was to evaluate the effectiveness of a cognitive motivational treatment program. METHOD: A randomized, controlled, single-blind clinical trial was carried out. A total of 104 patients were recruited to take part in the trial, of whom ultimately 62 patients were allocated into two groups and finished the study. An initial assessment was carried out before patients were randomly placed in one of two groups for the clinical trial: (a) PIPE program plus routine care; and (b) routine care only. Clinical assessments were performed at baseline at 6 months, 1 year and follow-ups, at 18 months and 5 years). RESULTS: MANCOVA analysis of tests repeated 18 months after the start of the intervention detected significant differences between the two groups in terms of clinical variables, everyday functioning and relapses. These differences remained upon follow-up measurements taken five years after the start of the trial. CONCLUSIONS: The present study offers scientific evidence for cognitive-motivational therapy's effectiveness as a treatment for clinical symptoms in the early stages of psychosis. PIPE intervention may contribute to long-term clinical improvement and stability.
Subject(s)
Cognitive Behavioral Therapy/methods , Motivational Interviewing/methods , Schizophrenia/diagnosis , Schizophrenia/therapy , Schizophrenic Psychology , Adult , Female , Follow-Up Studies , Humans , Male , Single-Blind Method , Time Factors , Treatment Outcome , Young AdultABSTRACT
Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.
ABSTRACT
Zircon-type holmium phosphate (HoPO4) and thulium phosphate (TmPO4) have been studied by single-crystal x-ray diffraction and ab initio calculations. We report on the influence of pressure on the crystal structure, and on the elastic and thermodynamic properties. The equation of state for both compounds is accurately determined. We have also obtained information on the polyhedral compressibility which is used to explain the anisotropic axial compressibility and the bulk compressibility. Both compounds are ductile and more resistive to volume compression than to shear deformation at all pressures. Furthermore, the elastic anisotropy is enhanced upon compression. Finally, the calculations indicate that the possible causes that make the zircon structure unstable are mechanical instabilities and the softening of a silent B 1u mode.
ABSTRACT
A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu(3+) nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu(3+) photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two (5)D0-->(7)F0 photoluminescence peaks confirms the existence of two local environments for Eu(3+), at least for the low-pressure phase. One environment is the expected for substituting Y(3+) and the other is likely a disordered environment possibly found at the surface of the nanoboxes.
ABSTRACT
We report an experimental and theoretical high-pressure study of the vibrational properties of synthetic monoclinic bismuth oxide (α-Bi(2)O(3): ), also known as mineral bismite. The comparison of Raman scattering measurements and theoretical lattice-dynamics ab initio calculations is key to understanding the complex vibrational properties of bismite. On one hand, calculations help in the symmetry assignment of phonons and to discover the phonon interactions taking place in this low-symmetry compound, which shows considerable phonon anticrossings; and, on the other hand, measurements help to validate the accuracy of first-principles calculations relating to this compound. We have also studied the pressure-induced amorphization (PIA) of synthetic bismite occurring around 20 GPa and showed that it is reversible below 25 GPa. Furthermore, a partial temperature-induced recrystallization (TIR) of the amorphous sample can be observed above 20 GPa upon heating to 200°C, thus evidencing that PIA at room temperature occurs because of the inability of the α phase to undergo a phase transition to a high-pressure phase. Raman scattering measurements of the TIR sample at room temperature during pressure release have been performed. The interpretation of these results in the light of ab initio calculations of the candidate phases at high pressures has allowed us to tentatively attribute the TIR phase to the recently found high-pressure hexagonal HPC phase and to discuss its lattice dynamics.
Subject(s)
Bismuth/chemistry , Models, Chemical , Models, Molecular , Computer Simulation , Materials Testing , Molecular Conformation , Phase Transition , Pressure , Transition Temperature , VibrationABSTRACT
An experimental and theoretical study of the structural properties of monoclinic bismuth oxide (α-Bi2O3) under high pressures is here reported. Both synthetic and mineral bismite powder samples have been compressed up to 45 GPa and their equations of state have been determined with angle-dispersive x-ray diffraction measurements. Experimental results have been also compared with theoretical calculations which suggest the possibility of several phase transitions below 10 GPa. However, experiments reveal only a pressure-induced amorphization between 15 and 25 GPa, depending on sample quality and deviatoric stresses. The amorphous phase has been followed up to 45 GPa and its nature discussed.
ABSTRACT
Order-disorder phase transitions induced by thermal annealing have been studied in the ordered-vacancy compound ZnGa2Se4 by means of Raman scattering and optical absorption measurements. The partially disordered as-grown sample with tetragonal defect stannite (DS) structure and I4¯2m space group has been subjected to controlled heating and cooling cycles. In situ Raman scattering measurements carried out during the whole annealing cycle show that annealing the sample to 400 °C results in a cation ordering in the sample, leading to the crystallization of the ordered tetragonal defect chalcopyrite (DC) structure with I4¯ space group. On decreasing temperature the ordered cation scheme of the DC phase can be retained at ambient conditions. The symmetry of the Raman-active modes in both DS and DC phases is discussed and the similarities and differences between the Raman spectra of the two phases emphasized. The ordered structure of annealed samples is confirmed by optical absorption measurements and ab initio calculations, that show that the direct bandgap of DC-ZnGa2Se4 is larger than that of DS-ZnGa2Se4.
ABSTRACT
OBJECTIVE: We studied the evolution of drug combinations used, as well as the clinical and immunological profile of patients at initiation of highly active antiretroviral therapy (HAART) between 1996 and 2006 in West Africa. SETTINGS AND METHOD: IeDEA West Africa is a network of HIV care programs established in 2006. We analyzed data from 12 clinical centers treating adults in five countries: Benin, Cote d'Ivoire, Senegal, Gambia, and Mali. Patients 16 years of age or over were included in the study and the following was documented: sex, date of birth and date of initiation of HAART. RESULTS: We included 14,496 adult patients having started HAART, among these 55 % had started HAART between 2005-2006. The proportion of HIV-infected women increased from 46 % in 1996-2000 to 63 % in 2005-2006. The median age at HAART initiation remained constant: 35 years for women and 40 years for men. The proportion of patients having started HAART with a CD4 count<200 cells/microl was 54 % in 1996-2000, and 64 % in 2005-2006. The most frequently prescribed HAART was: AZT/3TC (or d4T/DDI)/IDV (27 %) in 1996-2000; d4T (or AZT)/3TC/EFV (49 %) in 2003-2004, and d4T/3TC/NVP (49 %) in 2005-2006. CONCLUSION: The first line HAART regimen recommended by WHO was initiated in 83 % of cases in 2005-2006. New approaches to an earlier initiation of ART should be explored to reduce mortality in HIV-infected patients on HAART.
Subject(s)
Antiretroviral Therapy, Highly Active/trends , HIV Infections/drug therapy , Adult , Africa, Western , Female , Humans , Male , Middle Aged , Time FactorsABSTRACT
We present new experimental results on the formation of oxidants, such as hydrogen peroxide, ozone, and carbonic acid, under ion irradiation of icy mixtures of water/carbon dioxide at different ratios and temperatures (16 and 80 K). Pure water ice layers and mixtures with carbon dioxide were irradiated by 200 keV He+ ions. We found that the CO(2)/H(2)O ratio progressively decreased to a value of about 0.1, the H(2)O(2) production increased with increasing CO(2) abundance at both 16 and 80 K, and the CO and H(2)CO(3) production increased with increasing CO(2) abundance at 16 K. At 80 K, the synthesis of CO was less efficient because of the high volatility of the molecule that partially sublimed from the target. The production of carbonic acid was connected with the production of CO(3). O(3) was detected only after ion irradiation of CO(2)-rich mixtures. The experimental results are discussed with regard to the relevance they may have in the production of an energy source for a europan or a martian biosphere.
