Current fluctuations in nanopores: The effects of electrostatic and hydrodynamic interactions

Using nonequilibrium Langevin dynamics simulations of an electrolyte with explicit solvent particles, we investigate the effect of hydrodynamic interactions on the power spectrum of ionic nanopore currents. At low frequency, we find a power-law dependence of the power spectral density on the frequency, with an exponent depending on the ion density. Surprisingly, however, the exponent is not affected by the presence of the neutral solvent particles. We conclude that hydrodynamic interactions do not affect the shape of the power spectrum in the frequency range studied.     

Photon echoes stimulated from long-lived ordered populations in multi-level systems. The effect of intersystem crossing and optical branching

It is shown that the three pulse stimulated photon echo (3PSE) may be used to determine the yield for intersystem crossing in a guest molecule doped into a host lattice. An exact expression is derived for the intensity of the 3PSE for the case when all three spin sublevels participate in the optical pumping cycle. Yields for intersystem crossing in the systems naphthalene in durene (45%) and pentacene in naphthalene (15%) were obtained from the stimulated photon echo decay. In addition, the 3PSE formation is discussed in pseudo two-level systems where the level structure is caused by magnetic interactions. As an example, the 3PSE decay of the system triphenylmethyl in triphenylamine is analyzed.     

Optical dephasing in a glass-like system: a photon echo study of pentacene in benzoic acid

Optical absorption and picosecond photon echo experiments are used to study the dephasing of pentacene in benzoic acid. It is shown that, while the absorption spectrum of pentacene is effected by proton transfer in the benzoic acid dimer, the dephasing is caused by elastic and inelastic phonon scattering processes.     

Molecular hydrophobic attraction and ion-specific effects studied by molecular dynamics

Much is written about "hydrophobic forces" that act between solvated molecules and nonpolar interfaces, but it is not always clear what causes these forces and whether they should be labeled as hydrophobic. Hydrophobic effects roughly fall in two classes, those that are influenced by the addition of salt and those that are not. Bubble adsorption and cavitation effects plague experiments and simulations of interacting extended hydrophobic surfaces and lead to a strong, almost irreversible attraction that has little or no dependence on salt type and concentration. In this paper, we are concerned with hydrophobic interactions between single molecules and extended surfaces and try to elucidate the relation to electrostatic and ion-specific effects. For these nanoscopic hydrophobic forces, bubbles and cavitation effects play only a minor role and even if present cause no equilibration problems. In specific, we study the forced desorption of peptides from nonpolar interfaces by means of molecular dynamics simulations and determine the adsorption potential of mean force. The simulation results for peptides compare well with corresponding AFM experiments. An analysis of the various contributions to the total peptide-surface interactions shows that structural effects of water as well as van der Waals interactions between surface and peptide are important. Hofmeister ion effects are studied by separately determining the effective interaction of various ions with hydrophobic surfaces. An extension of the Poisson-Boltzmann equation that includes the ion-specific potential of mean force yields surface potentials, interfacial tensions, and effective interactions between hydrophobic surfaces. There, we also analyze the energetic contributions to the potential of mean force and find that the most important factor determining ion-specific adsorption at hydrophobic surfaces can best be described as surface-modified ion hydration.     

Hahn- and stimulated photon-echo decay measurements in the lowest doublet-doublet electronic transition of triphenylmethyl in triphenylamine

The results of Hahn (two-pulse) and stimulated (three-pulse) photon-echo decay measurements in the lowest ²A ← ²A electronic transition of triphenylmethyl in triphenylamine are reported and discussed. From the Zeeman effect on the photon-echo relaxation behaviour we conclude that hyperfine and superhyperfine interactions play a dominant role in the optical (phase) relaxation process.     

Four-wave mixing spectroscopy of molecular dimers. Application to dimers of pentacene in p-terphenyl

Dispersive coherent Stokes-Raman scattering (CSRS) experiments on pentacene dimers in p-terphenyl were performed to locate the corresponding singly excited, delocalized, dimer levels. In addition the CNRS technique was used to locate the doubly excited dimer state. Future experiments exploring the dynamics of this novel state are discussed.     

Graft-copolymerization of styrene on polypropylene in the solid phase

The graft-copolymerization of styrene on PP in the solid phase has been studied under various reaction conditions using a radical initiator. Polymerization kinetics were investigated by DSC experiments and reactions in glass ampoules. The conversion rate and grafting efficiency of styrene appeared to be strongly influenced by the presence of the PP matrix and the styrene/PP ratio. From reactions in a lab scale reactor the concentrations of styrene and initiator, the dosing rate and the temperature were investigated to be critical parameters determining the grafting efficiency and the average length and number of grafts. The phenomena observed were explained by describing the process in relative rates of diffusion and polymerization, including swelling of the polymer by styrene monomer and diffusion limitations (Trommsdorff effect).