A theoretical study of aqueous solvation of K comparing ab initio, polarizable, and fixed-charge models

The hydration of K(+) is studied using a hierarchy of theoretical approaches, including ab initio Born-Oppenheimer molecular dynamics and Car-Parrinello molecular dynamics, a polarizable force field model based on classical Drude oscillators, and a nonpolarizable fixed-charge potential based on the TIP3P water model. While models based more directly on quantum mechanics offer the possibility to account for complex electronic effects, polarizable and fixed-charges force fields allow for simulations of large systems and the calculation of thermodynamic observables with relatively modest computational costs. A particular emphasis is placed on investigating the sensitivity of the polarizable model to reproduce key aspects of aqueous K(+), such as the coordination structure, the bulk hydration free energy, and the self diffusion of K(+). It is generally found that, while the simple functional form of the polarizable Drude model imposes some restrictions on the range of properties that can simultaneously be fitted, the resulting hydration structure for aqueous K(+) agrees well with experiment and with more sophisticated computational models. A counterintuitive result, seen in Car-Parrinello molecular dynamics and in simulations with the Drude polarizable force field, is that the average induced molecular dipole of the water molecules within the first hydration shell around K(+) is slightly smaller than the corresponding value in the bulk. In final analysis, the perspective of K(+) hydration emerging from the various computational models is broadly consistent with experimental data, though at a finer level there remain a number of issues that should be resolved to further our ability in modeling ion hydration accurately.     

Critical Heat Flux for Downward Facing Boiling on a Coated Hemispherical Surface

An experimental study was performed to investigate the effect of surface coating on the critical heat flux for downward facing boiling on the outer surface of a hemispherical vessel. Steady-state boiling experiments were conducted in the subscale boundary layer boiling (SBLB) facility using test vessels with metallic microporous coatings to obtain the local boiling curves and the local critical heat flux (CHF) limits. Similar heat transfer performance was observed for microporous aluminum and microporous copper coatings. When compared to the corresponding data without coatings, the boiling curves for the coated vessels were found to shift upward and to the right. This meant that the CHF limit was higher with surface coating and that the minimum film boiling temperatures were located at higher wall superheats. In particular, the microporous coatings were found to enhance the local CHF values appreciably at all angular locations explored in the experiments. Results of the present study showed that the microporous aluminum coating was very durable. Even after many cycles of steady state boiling, the vessel coating remained rather intact, with no apparent changes in color or structure. Although similar heat transfer performance was observed for microporous copper coatings, the latter were found to be much less durable and tended to degrade after several cycles of boiling.     

Deterministic single-photon source for distributed quantum networking

A sequence of single photons is emitted on demand from a single three-level atom strongly coupled to a high-finesse optical cavity. The photons are generated by an adiabatically driven stimulated Raman transition between two atomic ground states, with the vacuum field of the cavity stimulating one branch of the transition, and laser pulses deterministically driving the other branch. This process is unitary and therefore intrinsically reversible, which is essential for quantum communication and networking, and the photons should be appropriate for all-optical quantum information processing.     

On a Question of Herman, Baker and Rippon Concerning Siegel Disks

Consider the family of exponential maps E_k(z) = exp(z)+k. Thispaper shows that any unbounded Siegel disk U of E_k containsthe singular value k on its boundary. By a result of Herman,this implies that k U if the rotation number is diophantine.2000 Mathematics Subject Classification 37F10, 30D05.     

Observation of cavity-mediated long-range light forces between strongly coupled atoms

We report on the observation of long-range forces between ultracold rubidium atoms that are mutually coupled by the field of a driven high-finesse optical cavity. Even for much less than one photon in the cavity on average, the forces strongly influence the spatial distribution of the atoms. This manifests itself as an asymmetric normal-mode spectrum of the strongly coupled atoms-cavity system. Expressions are given for the dipole force and the diffusion coefficient for the atoms in the presence of the other atoms. The data agree well with calculated spectra, which include the full motional dynamics of the many-atom system.     

Overtone spectroscopy of some benzaldehyde derivatives

Overtone spectrum of o, m and p-nitrobenzaldehydes and p-chlorobenzaldehyde has been studied in 2000–12000 cm⁻¹ region. Vibrational frequencies and anharmonicity constants for aryl as well as alkyl CH stretch vibrations have been determined. We have also determined the internuclear distances for the aryl CH bond in the different molecules. The small variation observed in these distances is an indication of the substitution effect. It is observed that in the case of p-disubstituted benzens, the shift in aryl CH bond is proportional to sum of the Hammet σ of the substituents. However in the case of o-disubstituted benzenes it is only 80% of the para-substituted shift.