Search results for "surface"

Harnessing Fluorescence versus Phosphorescence Branching Ratio in (Phenyl)n-Bridged (n = 0–5) Bimetallic Au(I) Complexes

2013

We have designed and synthesized a series of Au(I) complexes bearing either an alkynyl–(phenylene)n–diphosphine (A-0–A-3) or a (phenylene)n–diphosphine (B-1–B-5) bridge, among which the effective distance between Au(I) and the center of the emitting ππ* chromophore can be fine-tuned via the insertion of various numbers of phenylene spacers. We then demonstrated for the first time in a systematic manner the decrease of rate constant for S1 → T1 intersystem crossing (ISC) kisc as the increase of the effective distance. The results also unambiguously showed that the phosphorescence could be harvested via higher S0 → Sn (n > 1) electronic excitation, followed by fast Sn → Tm ISC and then the po…

2016

The photochemistry of benzophenone, a paradigmatic organic molecule for photosensitization, was investigated by means of surface-hopping ab initio molecular dynamics. Different mechanisms were found to be relevant within the first 600 fs after excitation; the long-debated direct (S1 → T1) and indirect (S1 → T2 → T1) mechanisms for population of the low-lying triplet state are both possible, with the latter being prevalent. Moreover, we established the existence of a kinetic equilibrium between the two triplet states, never observed before. This fact implies that a significant fraction of the overall population resides in T2, eventually allowing one to revisit the usual spectroscopic assignm…

Conformational equilibrium of chorismate. A QM/MM theoretical study combining statistical simulations and geometry optimisations in gas phase and in …

2003

We report a theoretical study on the conformational equilibrium of chorismate that precedes its rearrangement to prephenate, an important enzyme-catalyzed reaction. In first place we show that the usual classification of chorismate conformers based on the relative position of the hydroxyl and ether bridge, pseudo-diaxial and pseudo-diequatorial, is not the only relevant factor from the point of view of the a posteriori rearrangement. Here we also analyse another complementary geometrical classification based on the interatomic distance between the carbon atoms to be bounded. Using the umbrella sampling approach and this distance as distinguished internal reaction coordinate, the gas phase A…

Structure and properties ofn-alkyldimethylsilyl bonded silica reversed-phase packings

1978

Summary The effects of the modifier functionality and the chain length ofn-alkylchlorosilanes on the surface structure of packings and on their retention behaviour in reversed-phase chromatography were investigated. Comparative retention studies on three silica packings that had been treated to maximum conversion withn-octyltrichlorosilane (I),n-octylmethyldichlorosilane (II) andn-octyldimethylmonochlorosilane (III) showed that the most pronounced reversed-phase character is obtained by using III as the modifying reagent. A series ofn-alkyldimethylsilyl bonded silica packings were prepared with widely differingn-alkyl chain lengths. Although the packings are very hydrophobic, the maximum su…

Elemental contamination of an open-pit mining area in the Peruvian Andes

2014

New technologies and higher prices of raw materials have promoted the expansion of mining activity throughout the world; if not properly regulated, this activity can lead to contamination of the local and regional environ- ment. The city of Cerro de Pasco is located close to a large open-pit mine and in recent years, several reports have pro- vided evidence of environmental contamination and related health problems. The aim of this paper is to evaluate the contamination in fluvial water, sediments and biological fluids from this area. The collective results show elevated metal and metalloid concentrations in rivers and sediments, especially in the areas downstream of the mine. For instance,…

First-principles calculations on surface hydroxyl impurities in BaF2

2012

Abstract OH − impurities located near the (1 1 1) BaF 2 surface have been studied by using density functional theory (DFT) with hybrid exchange potentials, namely DFT-B3PW. Twenty surface OH − configurations were studied, and the hydroxyls located on the first surface layer are the energetically most favorable configurations. For the (1 1 1) BaF 2 surface atomic layers, the surface hydroxyls lead to a remarkable XY -translation and a dilating effect in the Z -direction, overcoming the surface shrinking effect in the perfect slab. Bond population analysis shows that the surface effect strengthens the covalency of surface OH − impurities. The studies on band structures and density of states (…

<em>Grid</em> poblacional 2011 para España. Evaluación metodológica de diversas posibilidades de elaboración

2017

Este trabajo presenta una evaluación, desde el punto de vista del usuario, de la malla regular (grid) de población, con resolución de 1 km2 , que el Instituto Nacional de Estadística (INE) ha hecho pública a partir de los resultados del Censo de Población y Viviendas 2011. Esta forma de difusión de resultados resulta muy novedosa y ofrece un gran valor analítico. Por primera vez esta información sobre la distribución espacial de la población se ha generado desde abajo (bottom-up) para el conjunto de España, es decir, a partir del conocimiento de las coordenadas de cada hogar, considerando como tales las del edificio donde reside. La disponibilidad de otra grid con idéntica resolución, elabo…

Origination and extinction patterns of mammals in three central Western Mediterranean islands from the Late Miocene to Quaternary

2008

Abstract An overview of the population histories of three insular realms (Gargano palaeo-archipelago, Sardinia–Maritime Tuscany palaeo-bioprovince and the Sicilian insular complex) during the Late Miocene and Quaternary are here presented. The complexity of biodiversity changes in the islands is analysed to propose an interpretation of origination and extinction patterns. The study highlighted several important aspects of insular faunas. Evolutionary radiations were found to contribute significantly only to the Gargano faunal diversity, likely because the area was an archipelago at the time. Another interesting result is that large and small mammals do not disperse and become extinct all at…

Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au130(pMBA)50

2015

Photodynamics of a highly monodisperse sample of a water-soluble gold nanocluster tentatively identified as Au130(pMBA)50 (pMBA = p-mercaptobenzoic acid) was studied by mid-IR transient absorption spectroscopy with visible excitation. The observed long-lived excited states (>1 ns) indicate a molecular behavior of the cluster. By combining the transient absorption data with DFT calculation results the observed relaxation dynamics could be fully explained by identifying several relaxation processes involving singlet and triplet manifolds. The results indicate that the cluster may have interesting transient magnetic properties due to a long-lived triplet population.

Comparison of mechanical properties and composition of magnetron sputter and plasma enhanced atomic layer deposition aluminum nitride films

2018

A comparative study of mechanical properties and elemental and structural composition was made for aluminum nitride thin films deposited with reactive magnetron sputtering and plasma enhanced atomic layer deposition (PEALD). The sputtered films were deposited on Si (100), Mo (110), and Al (111) oriented substrates to study the effect of substrate texture on film properties. For the PEALD trimethylaluminum–ammonia films, the effects of process parameters, such as temperature, bias voltage, and plasma gas (ammonia versus N2/H2), on the AlN properties were studied. All the AlN films had a nominal thickness of 100 nm. Time-of-flight elastic recoil detection analysis showed the sputtered films t…