Ion Chemistry in Atmospheric and Astrophysical Plasmas

There are many differences and also remarkable similarities between the ion chemistry and physics of planetary ionospheres and the ion chemistry and physics of astronomical environments beyond the solar system. In the early Universe, an expanded cooling gas of hydrogen and helium was embedded in the cosmic background radiation field and ionized by it. As the Universe cooled by adiabatic expansion, recombination occurred and molecular formation was driven by catalytic reactions involving the relict electrons and protons. Similar chemical processes are effective in the ionized zones of gaseous and planetary nebulae and in stellar winds where the ionization is due to radiation from the central stars, in the envelopes of supernovae where the ionization is initiated by the deposition of gamma-rays, in dissociative shocks where the ionization arises from electron impacts in a hot gas and in quasar broad-line region clouds where the quasar is responsible for the ionization. At high altitudes in the atmospheres of the Jovian planets, the main constituents are hydrogen and helium and the ion chemistry and physics is determined by the same processes, the source of the ionization being solar ultraviolet radiation and cosmic rays. After the collapse of the first distinct astronomical entities to emerge from the uniform flow, heavy elements were created by nuclear burning in the cores of the collapsed objects and distributed throughout the Universe by winds and explosions. The chemistry and physics became more complicated. Over 90 distinct molecular species have been identified in interstellar clouds where they are ionized globally by cosmic ray impacts and locally by radiation and shocks associated with star formation and evolution. Complex molecules have also been found in circumstellar shells of evolved stars. At intermediate and low altitudes in the Jovian atmospheres, the ion chemistry is complicated by the increasing abundance of heavy elements such as carbon, and an extensive array of complex molecules has been predicted. Reactions involving heavy elements dominate the structure of the ionspheres of the terrestrial planets and the satellites Titan and Triton

Van der Waals Interactions in DFT using Wannier Functions: improved C6C_6 and C3C_3 coefficients by a new approach

A new implementation is proposed for including van der Waals interactions in Density Functional Theory using the Maximally-Localized Wannier functions. With respect to the previous DFT/vdW-WF method, the present DFT/vdW-WF2 approach, which is based on the simpler London expression and takes into account the intrafragment overlap of the localized Wannier functions, leads to a considerable improvement in the evaluation of the $C_6$ van der Waals coefficients, as shown by the application to a set of selected dimers. Preliminary results on Ar on graphite and Ne on the Cu(111) metal surface suggest that also the $C_3$ coefficients, characterizing molecule-surfaces van der Waals interactions are better estimated with the new scheme.Comment: 5 pages, 2 table

Comment on ``A new efficient method for calculating perturbative energies using functions which are not square integrable'': regularization and justification

The method recently proposed by Skala and Cizek for calculating perturbation energies in a strict sense is ambiguous because it is expressed as a ratio of two quantities which are separately divergent. Even though this ratio comes out finite and gives the correct perturbation energies, the calculational process must be regularized to be justified. We examine one possible method of regularization and show that the proposed method gives traditional quantum mechanics results.Comment: 6 pages in REVTeX, no figure

The Ratio of Ortho- to Para-H2 in Photodissociation Regions

We discuss the ratio of ortho- to para-H2 in photodissociation regions (PDRs). We draw attention to an apparent confusion in the literature between the ortho-to-para ratio of molecules in FUV-pumped vibrationally excited states, and the H2 ortho-to-para abundance ratio. These ratios are not the same because the process of FUV-pumping of fluorescent H2 emission in PDRs occurs via optically thick absorption lines. Thus, gas with an equilibrium ratio of ortho- to para-H2 equal to 3 will yield FUV-pumped vibrationally excited ortho-to-para ratios smaller than 3, because the ortho-H2 pumping rates are preferentially reduced by optical depth effects. Indeed, if the ortho and para pumping lines are on the ``square root'' part of the curve-of-growth, then the expected ratio of ortho and para vibrational line strengths is the square root of 3, ~ 1.7, close to the typically observed value. Thus, contrary to what has sometimes been stated in the literature, most previous measurements of the ratio of ortho- to para-H2 in vibrationally excited states are entirely consistent with a total ortho-to-para ratio of 3, the equilibrium value for temperatures greater than 200 K. We present an analysis and several detailed models which illustrate the relationship between the total ratios of ortho- to para-H2 and the vibrationally excited ortho-to-para ratios in PDRs. Recent Infrared Space Observatory (ISO) measurements of pure rotational and vibrational H2 emissions from the PDR in the star-forming region S140 provide strong observational support for our conclusions.Comment: 23 pages (including 5 figures), LaTeX, uses aaspp4.sty, accepted for publication in Ap

Power-law carrier dynamics in semiconductor nanocrystals at nanosecond time scales

We report the observation of power law dynamics on nanosecond to microsecond time scales in the fluorescence decay from semiconductor nanocrystals, and draw a comparison between this behavior and power-law fluorescence blinking from single nanocrystals. The link is supported by comparison of blinking and lifetime data measured simultaneously from the same nanocrystal. Our results reveal that the power law coefficient changes little over the nine decades in time from 10 ns to 10 s, in contrast with the predictions of some diffusion based models of power law behavior.Comment: 3 pages, 2 figures, compressed for submission to Applied Physics Letter

Design and Additive Fabrication of Foot and Ankle-Foot Orthoses

Foot and ankle-foot orthoses are prescribed in order to promote mobility through supporting and/or realigning the lower leg and alleviating pain in the foot in different parts of the gait cycle. This paper will outline new approaches to the design and manufacture of personalised foot and ankle-foot orthoses (FO and AFO) using additive fabrication technology. The research is addressing the need for specific software design tools for orthosis design which enable their properties to be locally tailored within a mass customisation framework. Structure/material testing to support that activity is also being undertaken and will be described.Mechanical Engineerin

Syntheses and characterization of aryl-substituted pyrogallol[4]arenes and resorcin[4]arenes

Thirteen aryl-substituted pyrogallol[4]arene and resorcin[4]arenes structures are synthesized and characterized. The effect of the varying aryl pendent groups on π–π distance, the inward tilt of the pendent –R groups, the twist angle of the pendent –R groups, and the angle between the pendent –R groups is methodically investigated and discussed.</p

Theory of collision-induced translation-rotation spectra: H2-He

This is the published version, also available here: http://dx.doi.org/10.1103/PhysRevA.29.595.An adiabatic quantal theory of spectral line shapes in collision-induced absorption and emission is presented which incorporates the induced translation-rotation and translation-vibration spectra. The generalization to account for the anisotropy of the scattering potential is given. Calculations are carried out of the collision-induced absorption spectra of He in collisions with H2 with ab initio electric dipole functions and realistic potentials. The anisotropy of the interaction potential is small and is not included in the calculations. The predicted spectra are in satisfactory agreement with experimental data though some deviations occur which may be significant. The rotational line shapes have exponential wings and are not Lorentzian. The connection between the quantal and classical theories is written out explicitly for the isotropic overlap induction

Dirac's hole theory versus quantum field theory

Dirac's hole theory and quantum field theory are usually considered equivalent to each other. For models of a certain type, however, the equivalence may not hold as we discuss in this Letter. This problem is closely related to the validity of the Pauli principle in intermediate states of perturbation theory.Comment: No figure