Absorption and emission spectra of fluorescent silica nanoparticles from TD-DFT/MM/PCM calculations

A multi-scale computational protocol, which combines Quantum Mechanics and Molecular Mechanics (QM/MM) calculations with the polarisable continuum model (PCM), has been used to study the tetramethylrhodamine isothiocyanate (TRITC) fluorophore, embedded in three different environments, namely in water, on an amorphous silica surface and covalently encapsulated in a silica nanoparticle (C dot). Absorption and emission spectra have been simulated by using TD-B3LYP/PCM calculations, performed on the TRITC ground and excited state geometries, optimized at the QM/MM level. The results are in good agreement with experimental data confirming the caging effect played by the silica shell on the mobility of the TRITC molecule when covalently encapsulated in silica nanoparticles. This could result in a decrease of the nonradiative decay rate and thus an increase of the quantum yield of the molecule.     

Influence of the alkyl and alkoxy side chains on the electronic structure and charge-transport properties of polythiophene derivatives

Density Functional Theory has been used to study the structural, electronic and charge-transport properties of two regio-regular head-to-tail polythiophene derivatives, i.e. poly(3-hexyl-thiophene), P3HT, and poly(3-oxyhexyl-thiophene), P3OHT. The effect of substituents on the electronic structure was analyzed by means of bandwidth, bandgap, effective mass, total and partial densities of states and crystal orbital overlap populations. Electronic couplings were estimated from band diagrams as the splitting of the valence band. The neutral and cationic states of isolated oligomers were optimized using the supercell approximation. The hole-transfer rates and mobilities were evaluated according to Marcus's theory. Results provide a compelling illustration of the effect of side chains on the crystal packing, electronic structure and charge-transport properties. Thus, the hole mobility calculated for the alkyl derivative was 0.15 cm(2) V(-1) s(-1) (experimental mobility is 0.10 cm(2) V(-1) s(-1)), while the alkoxy derivative has a theoretical mobility of 0.49 cm(2) V(-1) s(-1). The obtained results hopefully could motivate experimentalists to try out P3OHT for an improved charge carrier mobility.     

Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids

Properties of the surface of ionic liquids, such as surface tension, ordering, and charge and density profiles, were studied using molecular simulation. Two types of modification in the molecular structure of imidazolium cations were studied: the length of the alkyl side chain and the presence of a polar hydroxyl group at the end of the side chain. Four ionic liquids were considered: 1-ethyl-3-methylimidazolium tetrafluoroborate, [C(2)C(1)im][BF(4)]; 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate, [C(2)OHC(1)im][BF(4)]; 1-octyl-3-methylimidazolium tetrafluoroborate, [C(8)C(1)im][BF(4)] and 1-(8-hydroxyoctyl)-3-methylimidazolium tetrafluoroborate, [C(8)OHC(1)im][BF(4)]. The surface tension was calculated using both mechanical and thermodynamic definitions, with consistent treatment of the long-range corrections. The simulations reproduce the available experimental values of surface tension with a maximum deviation of ±10%. This energetic characterization of the interface is completed by microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface. The presence of the hydroxyl group modifies the local structure at the interface, leading to a less organized liquid phase. The results allow us to relate the surface tension to the structural ordering at the liquid-vacuum interface.     

Fluorescence spectra of organic dyes in solution: a time dependent multilevel approach

Classical all-atom molecular dynamics (MD) simulations and quantum mechanical (QM) time-dependent density functional theory (TD-DFT) calculations are employed to study the conformational and photophysical properties of the first emitter excited state of tetramethyl-rhodamine iso-thiocyanate fluorophore in aqueous solution. For this purpose, a specific and accurate force field has been parameterised from QM data to model the fluorophore's first bright excited state. During the MD simulations, the consequences of the π→π* electronic transition on the structure and microsolvation sphere of the dye has been analysed in some detail and compared to the ground state behaviour. Thereafter, fluorescence has been calculated at the TD-DFT level on configurations sampled from the simulated MD trajectories, allowing us to include time dependent solvent effects in the computed emission spectrum. The latter, when compared with the absorption spectrum, reproduces well the experimental Stokes shift, further validating the proposed multilevel computational procedure.     

Radiative efficiencies for fluorinated esters: indirect global warming potentials of hydrofluoroethers

Density Functional Theory (DFT) has been used with an empirically-derived correction for the wavenumbers of vibrational band positions to predict the infrared spectra of several fluorinated esters (FESs). Radiative efficiencies (REs) were then determined using the method of Pinnock et al. and these were used with atmospheric lifetimes from the literature to determine the direct global warming potentials of FESs. FESs, in particular fluoroalkylacetates, alkylfluoroacetates and fluoroalkylformates, are potential greenhouse gases and their likely long atmospheric lifetimes and relatively large REs, compared to their parent HFEs, make them active contributors to global warming. Here, we use the concept of indirect global warming potential (indirect GWP) to assess the contribution to the warming of several commonly used HFEs emitted from the Earth's surface, explicitly taking into account that these HFEs will be converted into the corresponding FESs in the troposphere. The indirect GWP can be calculated using the radiative efficiencies and lifetimes of the HFE and its degradation FES products. We found that the GWPs of those studied HFEs which have the smallest direct GWP can be increased by 100-1600% when taking account of the cumulative effect due to the secondary FESs formed during HFE atmospheric oxidation. This effect may be particularly important for non-segregated HFEs and some segregated HFEs, which may contribute significantly more to global warming than can be concluded from examination of their direct GWPs.     

Selecting intervention strategies against eutrophication and the drastic decrease in bird abundance in Ringkøbing Fjord

Ringkøbing Fjord is a large and shallow brackish lagoon on the west coast of Denmark that has gone through two environmental regime shifts in recent decades. Different intervention strategies, including nutrient abatement and the construction of facilities to increase the water exchange between the lagoon and the outside sea, have been proposed to achieve good water quality in terms of trophic state and conditions for waterfowl. The selection of an intervention strategy is a complex decision-making problem in which several conflicting objectives, like costs of application and environmental or social impacts, must be taken into account simultaneously. We propose a PC-based decision support system, called the Generic Multi-Attribute Analysis system, to deal with such interdisciplinary analyses. It evaluates the intervention strategies by means of an additive multiattribute utility model accounting for imprecision of the various components of the analysis, such as intervention strategy performances and decision-makers’ preferences. Also, it implements what is known as decision making with partial information, through the application of Monte Carlo simulation techniques. This enables a straightforward analysis of the difference between an anthropocentrist and an ecocentrist view of the problem, from which a final recommendation can be reached.     

Integral formulas for compact spaceliken-submanifolds in de Sitter spaces applications to the parallel mean curvature vector case

We introduce a new method to study compact spaceliken-submanifolds in de Sitter spacesS _q ^n+q by means of certain integral formulas which have a very clear geometric meaning. As a first application of them we obtain a Bernstein type result for complete maximal submanifolds inS _q ^n+q . As for surfaces, we also get a uniqueness result for compact spacelike surfaces inS _q ^2+q with parallel mean curvature vector field. Partially supported by a DGICYT Grant No. PB91-0705-C02-02 Partially supported by a DGICYT Grant No. PB91-0731     

O-Alkylation of 3-hydroxy-1-phenyl-2-pyrazolin-5-one

3-Hydroxy-1-phenyl-2-pyrazolin-5-one 1 reacts with primary, secondary and allylic alcohols under catalytic acidic conditions and in the presence of 3 Å molecular sieves, to afford 3-alkoxy-1-phenyl-2-pyrazolin-5-ones 3 .