Cavity-induced modifications of molecular structure in the strong coupling regime

In most theoretical descriptions of collective strong coupling of organic molecules to a cavity mode, the molecules are modeled as simple two-level systems. This picture fails to describe the rich structure provided by their internal rovibrational (nuclear) degrees of freedom. We investigate a first-principles model that fully takes into account both electronic and nuclear degrees of freedom, allowing an exploration of the phenomenon of strong coupling from an entirely new perspective. First, we demonstrate the limitations of applicability of the Born-Oppenheimer approximation in strongly coupled molecule-cavity structures. For the case of two molecules, we also show how dark states, which within the two-level picture are effectively decoupled from the cavity, are indeed affected by the formation of collective strong coupling. Finally, we discuss ground-state modifications in the ultra-strong coupling regime and show that some molecular observables are affected by the collective coupling strength, while others only depend on the single-molecule coupling constant.Comment: 12 pages, 8 figure

The Eastward Enlargement of the Eurozone: Trade and FDI

Trade and FDI, Economic Integration

Sensitivity of peatland carbon loss to organic matter quality

Copyright © 2012. American Geophysical Union. All Rights Reserved.This is the published version of the article; Leifeld, J., M. Steffens, and A. Galego-Sala (2012), Sensitivity of peatland carbon loss to organic matter quality, Geophys. Res. Lett., 39, L14704, doi:10.1029/2012GL051856.Peatland soils store substantial amounts of organic matter (OM). During peat formation, easily decomposable OM is preferentially lost and more recalcitrant moieties accumulate. In a peat profile, OM quality thus scales with depth. Drainage and ongoing climate change poses the risk of rapid OM loss when formerly anoxic peat layers oxidize. During peat decomposition, deeper, more recalcitrant peat is exposed to the oxygen-rich surface, which may influence the decomposition rate. We show that the soil respiration rate of a disturbed temperate peatland is strongly controlled by the peat's quality and especially its polysaccharides content. The polysaccharide content of soil profiles in a wider range of peatland sites with differing degrees of disturbance was inferred by means of solid-state13C NMR and DRIFT spectroscopy. The data confirmed a strong decline in polysaccharide content with depth and a poor OM quality of surface peat in soils drained decades ago. We combined the evidence from respiration and spectroscopic measurements to deduce the sensitivity of peatland carbon loss with respect to OM quality by scaling measured quality to a 142-years record of peatland subsidence and carbon loss at one of the sites. According to the functional relationship between quality and respiration, the measured average annual carbon loss rate of 2.5 t C ha−1 at that site was 20 t C ha−1 at the onset of peatland drainage and dropped to less than 1 t C ha−1 in recent times

Polaritonic Chemistry with organic molecules

This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Photonics, copyright © 2017 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acsphotonics.7b00680We present an overview of the general concepts of polaritonic chemistry with organic molecules, i.e., the manipulation of chemical structure that can be achieved through strong coupling between confined light modes and organic molecules. Strong coupling and the associated formation of polaritons, hybrid light-matter excitations, lead to energy shifts in such systems that can amount to a large fraction of the uncoupled transition energy. This has recently been shown to significantly alter the chemical structure of the coupled molecules, which opens the possibility to manipulate and control reactions. We discuss the current state of theory for describing these changes and present several applications, with a particular focus on the collective effects observed when many molecules are involved in strong couplingThis work has been funded by the European Research Council under grant agreements ERC-2011-AdG-290981 and ERC-2016-STG- 714870, by the European Union Seventh Frame-work Programme under grant agreement FP7-PEOPLE-2013-CIG-618229, and the Spanish MINECO under contractMAT2014-53432-C5-5-R and the“María de Maeztu”programfor Units of Excellence in R&D (MDM-2014-0377)

Many-molecule reaction triggered by a single photon in polaritonic chemistry

The second law of photochemistry states that, in most cases, no more than one molecule is activated for an excited-state reaction for each photon absorbed by a collection of molecules. In this Letter, we demonstrate that it is possible to trigger a many-molecule reaction using only one photon by strongly coupling the molecular ensemble to a confined light mode. The collective nature of the resulting hybrid states of the system (the so-called polaritons) leads to the formation of a polaritonic "supermolecule" involving the degrees of freedom of all molecules, opening a reaction path on which all involved molecules undergo a chemical transformation. We theoretically investigate the system conditions for this effect to take place and be enhanced.This work has been funded by the European Research Council under Grants No. ERC-2011-AdG-290981 and No. ERC- 2016-STG-714870, by the European Union Seventh Framework Programme under Grant No. FP7-PEOPLE- 2013-CIG-618229, and the Spanish MINECO under Contract No. MAT2014-53432-C5-5-R and the “María de Maeztu” program for Units of Excellence in R&D (MDM-2014-0377)

Cavity Casimir-Polder Forces and Their Effects in Ground-State Chemical Reactivity

Here, we present a fundamental study on how the ground-state chemical reactivity of a single molecule can be modified in a QED scenario, i.e., when it is placed inside a nanoscale cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic, and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in the present scenario, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respect to the cavity fieldThis work has been funded by the European Research Council (ERC-2016-STG-714870) and the Spanish MINECO under Contract No. MAT2014-53432-C5-5-R and the “María de Maeztu” program for Units of Excellence in R&D (MDM-2014-0377), as well as through a Ramón y Cajal grant (J. F.

To be or not to be hospitalised with tuberculosis in Portugal

SETTING: In Portugal, as in other countries, tuberculosis (TB) is considered a disease that should be managed on an ambulatory basis. However, hospitalisation remains important to manage some at-risk groups and complications. OBJECTIVE: To identify the possible risk factors associated with hospitalisations in TB patients in Portugal. DESIGN: Data extraction through two national databases (one for registration of TB cases and the other with hospitalisation information in public health facilities) between 2007 and 2013. Univariate and multivariate analysis of demographic and clinical variables was performed. RESULTS: We identified 4421 hospitalisations. Chronic diseases, cancer, substance abuse, a higher social/economic risk, extra-pulmonary TB, lung cavitary disease and previous uncompleted treatment were more frequent among hospitalised patients. Human immunodeficiency virus coinfection, cancer, alcohol abuse, extra-pulmonary TB and uncompleted previous TB treatment were the most important predictors of hospitalisation with TB. The hospitalisation rate among TB patients in Portugal was lower when compared with other countries with lower and higher incidences. CONCLUSION: Immune dysfunctions and progression of chronic diseases are associated with more severe forms of TB and frequent adverse effects which can be sufficiently severe to necessitate hospital admission. Despite having an intermediate TB incidence, the hospitalisation rate in Portugal is not higher than that of other countries

Downbeat Nystagmus in Episodic Ataxia Type 1 Associated with a Novel KCNA1 Mutation

info:eu-repo/semantics/publishedVersio

Anthropogenic features in the Sines (Portugal) and Essaouira (Morocco) coastal aquifers: a comparative study of their hydrochemical evolution by a Principal Component Analysis.

Considering the effects of climatic conditions on groundwater resources salinization and quality, a comparative study was conducted on the coastal aquifers of Sines (Portugal) and Essaouira (Morocco). Under the climatic and environmental conditions these two basins present different vulnerabilities to anthropogenic activities. Both aquifers correspond to sedimentary basins with similar structures and lithologies. From the available physical, chemical and piezometric data, two series of results of each area were selected corresponding to two different years that were analysed by Principal Component Analysis (PCA). Sines basin is characterised by a temperate climate. In the Sines aquifer the waterrock interaction process is the major mechanism responsible for the groundwater evolution, conferring a calcium-bicarbonate facies. Applying the PCA, punctual anthropogenic contamination was identified and linked to agricultural activities. The water resources of the Essaouira basin are characteristic of a semi-arid climate, and are severely impacted by the climate (quantity and quality). PCA allowed the evaluation of the contribution of the Tidzi diapir in the water recharge that confers to the groundwater a sodium-chloride facies. Although this statistical method did not shown a nitrate contamination input in the Essaouira multi-aquifer, this polluent presents locally high values. Also the very high evaporation and scarce precipitation activate the processes of salinization and contamination.Considerando los efectos de las condiciones climáticas sobre la calidad y la salinidad de las aguas subterráneas, se ha llevado a cabo un estudio comparativo entre los acuíferos costeros de Sines (Portugal) y de Essaouira (Marruecos). Teniendo en cuenta las condiciones climáticas y el medio ambiente de estas dos cuencas, resultan distintas vulnerabilidades a las actividades antrópicas. Ambos acuíferos se localizan en cuencas sedimentarias de estructura y de litología idénticas. Un Análisis de Componentes Principales fue realizado a partir de datos físicos, químicos y piezométricos conseguidos durante dos años en cada área. La cuenca de Sines se caracteriza por un clima templado. En el acuífero de Sines el desarrollo de las interacciones agua-roca es mayoritariamente responsable de la modificación de las aguas subterráneas, confiriendo una facies calcio-bicarbonatada. Mediante un Análisis de Componentes Principales, se identificó una contaminación antropogénica puntual de origen agrícola. Los recursos en agua de la cuenca de Essaouira están dentro de un clima semiárido, dependiendo muchísimo de este (cantidad y calidad). La utilización de la citada metodología permitió evidenciar la contribución del diapiro Tidzi en las aguas de recargas, confiriendo una facies de cloruro sódico en las aguas subterráneas. Aunque este método estadístico no permitió la demostración de la contaminación por los nitratos en los diversos acuíferos de Essaouira, aquel contaminante se encontraba puntualmente en altas concentraciones. Por otra parte, la fuerte evaporación y las bajas precipitaciones amplían el fenómeno de salinidad y de contaminación