Search results for "General Physics"
showing 10 items of 13583 documents
Interaction between nitroxyl radicals and CdTe quantum dots: Determination of fluorescence-quenching mechanisms in aqueous solution
2019
Abstract The present work characterizes the optical properties of CdTe quantum dots (CdTe QDs) after interaction with nitroxyl radicals based on steady-state and time-resolved fluorescence spectroscopy studies. QDs of different sizes were exposed to 2 different nitroxyl radicals, i.e., TEMPO and 4-amino-TEMPO radicals. A clear dependence of dynamic and static Stern-Volmer constants values, KD and KS, respectively, was observed as a function of the size of QDs used, with a change from a mostly static mechanism (for smaller QD sizes) to a dynamic mechanism predominating as the nanoparticles increase in size. All observed effects are dependent on both the concentration of the radical and the s…
Photophysics and photostability of adenine in aqueous solution: A theoretical study
2010
Abstract The sequential Monte Carlo/CASPT2 approach was employed to investigate deactivation and emission processes from the lowest-lying ππ∗ and n π∗ excited states of 9H-adenine in aqueous solution. It is found that conical intersections connecting the ππ∗ and n π∗ states with the ground state are also present in solution, whereas the barriers for the deactivation paths are significantly smaller on solvated conditions. The large destabilization of the n π∗ state found in solution possibly prevents its involvement in the deactivation photophysics and explains the change from a bi- to a mono-exponential decay for the molecule in the gas phase and solution, respectively.
Molecular dynamics and metadynamics simulations of electrosprayed water nanodroplets including sodium bis(2-ethylhexyl)sulfosuccinate micelles.
2017
The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) under conditions of electrospray ionization (ESI) has been investigated by molecular dynamics (MD) and well-tempered metadynamics (WTM) simulations at 300 K and 400 K. We have examined water droplets with initial fixed numbers of water molecules (1000) and AOT− anions (100), and with sodium cations in the range of 70–130. At 300 K, all charged droplets show the water evaporation rate increasing with the absolute value of the initial droplet charge state (Z), accompanied by ejection of an increasing number of solvated sodium ions or by expulsion of AOT− anions depending on the sign of Z and by fragmentation i…
Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution
2011
Femtosecond-resolved broadband fluorescence studies are reported for[ M(bpy)(3)](2+) (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [ Fe(bpy)(3)](2+) and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the (MLCT)-M-1 fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in <= 30-45 fs due to intersystem crossing to the (MLCT)-M-3 states, but a longer lived component of similar to 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are character…
A quantum mechanics-molecular mechanics study of dissociative electron transfer : The methylchloride radical anion in aqueous solution
2002
The dissociative electron transfer reaction CH3Cl+e−→CH3•+Cl− in aqueous solution is studied by using a QM/MM method. In this work the quantum subsystem (a methylchloride molecule plus an electron) is described using density functional theory while the solvent (300 water molecules) is described using the TIP3P classical potential. By means of molecular dynamics simulations and the thermodynamic integration technique we obtained the potential of mean force (PMF) for the carbon–chlorine bond dissociation of the neutral and radical anion species. Combining these two free energy curves we found a quadratic dependence of the activation free energy on the reaction free energy in agreement with Ma…
Molecular simulation studies of water physisorption in zeolites
2006
We report a series of Grand Canonical Monte Carlo simulations of water adsorption in NaY and NaX faujasite, as well as in silicalite-1. Computed adsorption isotherms and heats of adsorption were in good agreement with the available experiments. The existence of cyclic water hexamers in NaX located in the 12-ring windows, recently disclosed by neutron diffraction experiments (Hunger et al., J. Phys. Chem. B, 2006, 110, 342-353) was reproduced in our simulations. Interestingly enough, such cyclic hexamer clusters were also observed in the case of NaY, in which no stabilizing cation is present in the 12-ring window. We also report cation redistribution upon water adsorption for sodium faujasit…
Photocatalytic activity of transition-metal-loaded titanium(IV) oxide powders suspended in aqueous solutions: Correlation with electron–hole recombin…
2001
Photocatalytic reactions by transition-metal (V, Cr, Fe, Co, Cu, Mo, or W) loaded TiO2 (M-TiO2) powders suspended in aqueous solutions of methanol, (S)-lysine (Lys), or acetic acid were investigated. The photoactivities of various samples were compared with the rate constant (kr) of recombination of photoexcited electrons and positive holes determined by femtosecond pump–probe diffuse reflection spectroscopy (PP-DRS). As a general trend, increased loading decreased the rate of formation of the main products (H2 , pipecolinic acid (PCA), and CO2) under UV (>300 nm) irradiation, and the effect became more intense on increasing the loading. In PP-DRS, these M-TiO2 gave similar decays of absorp…
Photocatalytic oxidation of toluene on irradiated TiO2: comparison of degradation performance in humidified air, in water and in water containing a z…
2003
Photocatalytic degradation of toluene was carried out both in gas–solid and in liquid–solid regime by using polycrystalline samples of TiO2 Merck and TiO2 Degussa P25. For the gas–solid regime two types of continuous photoreactor were used, a fixed bed one of cylindrical shape and a Carberry type photoreactor, both irradiated by near-UV light. The inlet reacting mixture consisted of air containing toluene and water vapours. The influence of the gas flow rate and the presence of water vapour on the photocatalytic process was investigated. CO2 and benzaldehyde were the toluene degradation products detected in the gas phase by using TiO2 Merck. In the presence of water vapour this catalyst exh…
Apparent molar volumes of lithium nitrate in 1-propanol + water in the temperature range from 288.15 to 318.15 K
2002
Abstract Densities of 1-propanol+water+lithium chloride mixtures have been measured with an oscillating-tube densimeter over a large range of concentrations of the salt and 1-propanol at 288.15, 298.15, 308.15, and 318.15 K. From these densities, apparent molar volumes of lithium chloride in 1-propanol+water mixtures have been calculated for each temperature, and apparent molar volumes at infinite dilution have been evaluated. An empirical correlation for partial molar volumes of lithium chloride in 1-propanol+water mixtures with solvent composition and temperature has been derived.
Modes of motion in a confined colloidal suspension under shear
2004
We investigated aqueous suspensions of charged polystyrene latex spheres at low salt concentration under the combined influence of steady shear and confining walls. Their equilibrium structure was adjusted via the particle and salt concentration to be either fluid or body centred cubic. Using high-resolution real-space microscopy, we here present a first direct observation of collective modes of motion under shear. As a function of either shear rate and/or salt concentration, we find a continuous transition from registered to free sliding of layers accompanied by an equally continuous structural rearrangement lowering the dimensionality of long-ranged order.