A Unified Theoretical Description of the Thermodynamical Properties of Spin Crossover with Magnetic Interactions

After the discovery of the phenomena of light-induced excited spin state trapping (LIESST), the functional properties of metal complexes have been studied intensively. Among them, cooperative phenomena involving low spin-high spin (spin-crossover) transition and magnetic ordering have attracted interests, and it has become necessary to formulate a unified description of both phenomena. In this work, we propose a model in which they can be treated simultaneously by extending the Wajnflasz-Pick model including a magnetic interaction. We found that this new model is equivalent to Blume-Emery-Griffiths (BEG) Hamiltonian with degenerate levels. This model provides a unified description of the thermodynamic properties associated with various types of systems, such as spin-crossover (SC) solids and Prussian blue analogues (PBA). Here, the high spin fraction and the magnetization are the order parameters describing the cooperative phenomena of the model. We present several typical temperature dependences of the order parameters and we determine the phase diagram of the system using the mean-field theory and Monte Carlo simulations. We found that the magnetic interaction drives the SC transition leading to re-entrant magnetic and first-order SC transitions.Comment: 30pages, 11figure

Programmatic feasibility of dried blood spots for the virological follow-up of patients on antiretroviral treatment in Nord Kivu, Democratic Republic of the Congo

Background:As part of its policy to shift monitoring of antiretroviral therapy (ART) to primary health care (PHC) workers, the Ministry of Health of the Democratic Republic of Congo (DRC) tested the feasibility of using dried blood spots (DBS) for viral load (VL) quantification and genotypic drug resistance testing in off-site high-throughput laboratories.Methods:DBS samples from adults on ART were collected in 13 decentralized PHC facilities in the Nord-Kivu province and shipped during program quarterly supervision to a reference laboratory 2000 km away, where VL was quantified with a commercial assay (m2000rt, Abbott). A second DBS was sent to a World Health Organization (WHO)-accredited laboratory for repeat VL quantification on a subset of samples with a generic assay (Biocentric) and genotypic drug resistance testing when VL >1000 copies per milliliter.Findings:Constraints arose because of an interruption in national laboratory funding rather than to technical or logistic problems. All samples were assessed by both VL assays to allow ART adjustment. Median DBS turnaround time was 37 days (interquartile range: 9-59). Assays performed unequally with DBS, impacting clinical decisions, quality assurance, and overall cost-effectiveness. Based on m2000rt or generic assay, 31.3% of patients were on virological failure (VF) and 14.8% presented resistance mutations versus 50.3% and 15.4%, respectively.Conclusion:This study confirms that current technologies involving DBS make virological monitoring of ART possible at PHC level, including in challenging environments, provided organizational issues are addressed. Adequate core funding of HIV laboratories and adapted choice of VL assays require urgent attention to control resistance to ART as coverage expands

Évolution géologique de la marge ouest-ibérique

This paper is a summary of the results of the authors recent researches about the Western Iberian continental margin. During the Mesozoic, the margin is affected by two consecutive extensional phases interpreted as the result from two episodes of rifting in the Atlantic. Then during Cenozoic, subsidence was interrupted by compression and related deformation, specially during Eocene time. Ante-mesozoic basement controls the structural and sedimentary evolution of the margin

New Gravity Map of the Western Galicia Margin:The Spanish Exclusive Economic Zone Project

Since 1995, the most intensive mapping of the seafloor off the Spanish coast has been carried out in the framework of the Spanish Exclusive Economic Zone Project (ZEEE).The main objectives of this project are to obtain improved multibeam bathymetric cartography of the areas off Spanish coastlines, and to perform a geophysical survey,well-suited with a 10-knot navigation velocity (some techniques requires lower navigation velocity). The geophysical survey includes gravity, geomagnetism, and low-penetration seismic techniques in order to infer the geological structure of the seafloor. Other oceanographic variables such as current, surface salinity, and temperature profiles, can be recorded without compromising this systematic survey effort. The ZEEE Project has carried out its survey activities for one month every year.Data acquisition is achieved aboard the Spanish R/V Hesperides. Until 1997, surveying efforts concentrated on the Balearic Sea and Valencia Gulf, both in the western Mediterranean Sea. Between 1998 and 2000, the ZEEE Project investigations were conducted offshore the Canary Archipelago. Since 2001, the third phase of the program has been focused on the West Galicia Margin in the northeastern Atlantic Ocean. Survey results on the West Galicia Margin area are of interest for two key reasons. First, there is great scientific interest in the improvement of the knowledge of this non-volcanic rifting margin, since this margin offers good conditions for the study of the processes that take place in this type of geological context,because it is sediment-starved. Second, the obtained results also have major socioeconomic repercussions because they can prove significant to defining the expansion of the Spanish shelf,beyond Spain’s Economic Exclusive Zone distance of 200 nautical miles. All of the gravity data acquired to date on this area have been stored as a database, with the aim of preparing gravity anomaly maps on a scale 1:200,000.The database and gravity anomaly charts from the ZEEE Project will provide the most coherent and complete gravity perspective available for this area. This article describes the efforts and accomplishments of the project to date

Overview of the recent operation of the AAC and LEAR for the low-energy antiproton physics programme

This paper reviews the recent performance of the AAC and LEAR. Activities on the AAC include the successful exploitation of a magnetic horn as an antiproton collector lens and an energy-saving mode of operation, which has been possible since 1992, when LEAR became the only client of the AAC. LEAR worked in its full momentum range between 100 MeV/c and 2 GeV/c, with perform-ance (intensities, ejection modes and spill length) exceeding the design specifications. Improvements are described, which contributed to the quality of the beam delivered to experiments. The reliability and availability of the antiproton machines are also discussed

The formation of passive margins: constraints from the crustal structure and segmentation of the deep Galicia margin, Spain

The crustal structure of the Mesozoic deep Galicia margin and adjacent ocean-continent boundary (OCB) was investigated by seismic reflection (including pre-stack depth migration and attenuation of seismic waves with time). The seismic data were calibrated using numerous geological samples recovered by drilling and/or by diving with submersible. The N-S trending margin and OCB are divided in two distinct segments by NE-SW synrift transverse faults locally reactivated and inverted by Cenozoic tectonics. The transverse faulting and OCB segmentation result from crustal stretching probably in a NE-SW direction during the rifting stage of the margin in early Cretaceous times. The Cenozoic tectonics are related to Iberia-Eurasia convergence in Palaeogene times (Pyrenean event). In both segments of the deep margin, the seismic crust is made of four horizontal layers: (1) two sedimentary layers corresponding to post- and syn-rift sequences, where velocity ranges from 1.9 to 3.5 km s−1, and where the Q factor is low, the two sedimentary layers being separated by a strong reflector marking the break-up unconformity; (2) a faulted layer, where velocity ranges from 4.0 to 5.2 km s−1, and where the Q factor is high. This layer corresponds to the margin tilted blocks, where continental basement and lithified pre-rift sediments were sampled; (3) the lower seismic crust, where the velocity (7 km s−1 and more) and the Q factor are the highest. This layer, probably made of partly serpentinized peridotite, is roofed by a strong S-S’ seismic reflector, and resting on a scattering, poorly reflective Moho. A composite model, based both on analogue modelling of lithosphere stretching and on available structural data, accounts for the present structure of the margin and OCB. Stretching and thinning of the lithosphere are accommodated by boudinage of the brittle levels (upper crust and uppermost mantle) and by simple shear in the ductile levels (lower crust and upper lithospheric mantle). Two main conjugate shear zones may account for the observations and seismic data: one (SZ1), located in the lower ductile continental crust, is synthetic to the tilting sense of the margin crustal blocks; another (SZ2), located in the ductile mantle, accounts for the deformation of mantle terranes and their final unroofing and exposure at the continental rift axis (now the OCB). The S-S′ reflector is interpreted as the seismic signature of the tectonic contact between crustal terranes and mantle rocks partly transformed into serpentinite by syn-rift hydrothermal activity. It is probably related to both shear zones SZ1 and SZ2. The seismic Moho is lower within the lithosphere, at the fresh-serpentinized peridotite boundary

Pressure-induced switching properties of the iron(iii) spin-transition complex [FeIII(3-OMeSalEen)2]PF6

We investigated the effect of an externally applied pressure on the iron(III) Schiff-base compound [Fe(3-OMeSalEen)2]PF6 (H-3-OMeSalEen, condensation product of 3-methoxy-substituted salicylaldehyde and N-ethylethylenediamine), which at ambient pressure displays a thermal spin transition with a 3 K wide hysteresis loop centered at 164 K. Raman spectrometry revealed the occurrence of a complete spin-state switching process for a pressure of P1/2 = 8–9 kbar at room temperature. The evolution of lattice parameters as a function of pressure was followed by X-ray diffraction measurements on single crystals, highlighting the important microscopic aspects at the origin of the pressure-induced transition, i.e. an anisotropic response and a high compressibility of the HS molecular lattice. Variable temperature magnetic susceptibility measurements at different applied pressures revealed the smoothening of the spin transition curves and a linear increase of the transition temperatures by ca. 16.4 (1.0) K kbar?1, in good agreement with the Clausius–Clapeyron law. The non-negligible influence of the pressure transmitting oils on the intrinsic transition properties was also evidenced and attributed to mechanical interactions between the particles and the solidified matrix

Molecular-scale dynamics of light-induced spin cross-over in a two-dimensional layer

Spin cross-over molecules show the unique ability to switch between two spin states when submitted to external stimuli such as temperature, light or voltage. If controlled at the molecular scale, such switches would be of great interest for the development of genuine molecular devices in spintronics, sensing and for nanomechanics. Unfortunately, up to now, little is known on the behaviour of spin cross-over molecules organized in two dimensions and their ability to show cooperative transformation. Here we demonstrate that a combination of scanning tunnelling microscopy measurements and ab initio calculations allows discriminating unambiguously between both states by local vibrational spectroscopy. We also show that a single layer of spin cross-over molecules in contact with a metallic surface displays light-induced collective processes between two ordered mixed spin-state phases with two distinct timescale dynamics. These results open a way to molecular scale control of two-dimensional spin cross-over layers