Anion binding by bambus[6]uril probed in the gas phase and in solution

Electrospray ionization mass spectrometry (ESI-MS) is used to probe the binding of small anions to the macrocycle of bambus[6]uril. For the halide ions, the experimental patterns suggest F(-) < Cl(-) < Br(-) < I(-), which is consistent with the order of anion binding found in the condensed phase. Parallel equilibrium studies in the condensed phase establish the association constants of halide anions and bambus[6]uril in mixed solvents. A detailed analysis of the mass spectrometric data is used to shed light on the correlations between the binding constants in the condensed phase and the ion abundances observed using ESI-MS. From the analysis it becomes apparent that ESI-MS can indeed represent the situation in solution to some extent, but the sampling in the gas-phase experiment is not 1:1 compared to that in solution.     

The C-O stretch as an unprecedently large spectral marker for the electron transfer between Copper(II) and a phenolate anion

An unprecedented red shift of more than 200 cm(-1) in the vibrational frequency of the C-O bond in the [Cu(PhO)Ln]+ complex (PhO = phenoxy), dependent on the number n of additional ligands L, is reported. Upon change of n from 1 to 2, the spin density is shifted from the aromatic ring to the oxygen and copper atoms, which is reflected in the bond order and thus vibrational frequency of the C-O bond.     

Structure and dynamics of dodecaborate clusters in water

We have studied using molecular dynamics simulations the interaction of the dodecaborate anion, B(12)H(12)(2-), and its amino, trimethyl, and triethyl derivatives with water molecules. We found peculiar organization of the water molecules in the first solvation shell with the formation of a dihydrogen bond between the hydrogen atoms of the anions and the hydrogen atoms of the water molecules. The simulations also show that the organization of the hydration shell is strongly influenced by the substituents in the anions. These differences are likely to play an important role in understanding the interaction of the anions with biological systems like membranes and proteins in aqueous environments.     

On the classical limit of Bohmian mechanics for Hagedorn wave packets

We consider the classical limit of quantum mechanics in terms of Bohmian trajectories. For wave packets as defined by Hagedorn we show that the Bohmian trajectories converge to Newtonian trajectories in probability.     

Ultimate state of thermal convection

The ultimate regime of thermal convection, the so-called Kraichnan regime [R. H. Kraichnan, Phys. Fluids 5, 1374 (1962)]], hitherto has been elusive. Here numerical evidence for that regime is presented by performing simulations of the bulk of turbulence only, eliminating the thermal and kinetic boundary layers and replacing them with periodic boundary conditions.     

Quantifying turbulence-induced segregation of inertial particles

Particles with different density from the advecting turbulent fluids cluster due to the different response of light and heavy particles to turbulent fluctuations. This study focuses on the quantitative characterization of the segregation of dilute polydisperse inertial particles evolving in turbulent flow, as obtained from direct numerical simulation of homogeneous isotropic turbulence. We introduce an indicator of segregation amongst particles of different inertia and/or size, from which a length scale r_{seg}, quantifying the segregation degree between two particle types, is deduced.     

The Smoluchowski limit for a simple mechanical model

We consider a vertical stick constantly accelerated along thex-axis by a forceF and which elastically collides with point particles of the same mass (atoms). The atoms are initially Poisson distributed and are allowed to have four velocities only. It is shown that under suitable scaling of the system the displacementQ(t) of the stick satisfies a nontrivial CLT:Q(t)=vFt+D ^1/2 W(t) (Smoluchowski equation), where the values ofv andD depend on the fact that one atom may collide several times.