Modulation of neutral interstellar He, Ne, O in the heliosphere. Survival probabilities and abundances at IBEX

Direct sampling of neutral interstellar (NIS) atoms by the Interstellar Boundary Explorer (IBEX) can potentially provide a complementary method for studying element abundances in the Local Interstellar Cloud and processes in the heliosphere interface.}{We set the stage for abundance-aimed in-depth analysis of measurements of NIS He, Ne, and O by IBEX and determine systematic differences between abundances derived from various calculation methods and their uncertainties.}{Using a model of ionization rates of the NIS species in the heliosphere, based on independent measurements of the solar wind and solar EUV radiation, we develop a time-dependent method of calculating the survival probabilities of NIS atoms from the termination shock (TS) of the solar wind to IBEX. With them, we calculate densities of these species along the Earth's orbit and simulate the fluxes of NIS species as observed by IBEX. We study pairwise ratios of survival probabilities, densities and fluxes of NIS species at IBEX to calculate correction factors for inferring the abundances at TS.}{The analytic method to calculate the survival probabilities gives acceptable results only for He and Ne during low solar activity. For the remaining portions of the solar cycle, and at all times for O, a fully time dependent model should be used. Electron impact ionization is surprisingly important for NIS O. Interpreting the IBEX observations using the time dependent model yields the LIC Ne/O abundance of $0.16\pm40$. The uncertainty is mostly due to uncertainties in the ionization rates and in the NIS gas flow vector.}{The Ne/He, O/He and Ne/O ratios for survival probabilities, local densities, and fluxes scaled to TS systematically differ and thus an analysis based only on survival probabilities or densities is not recommended, except the Ne/O abundance for observations at low solar activity.Comment: Astronomy & Astrophysics, in press. Language and editing corrections implemente

Influence of roughness on ZDDP tribofilm formation in boundary lubricated fretting

Influence of initial surface topography on tribofilm formation in ZDDP lubricated contact was analysed. A small displacement fretting tests with sinusoidal motion were carried out in classical sphere/plane configuration. A range of surfaces with different initial roughness were prepared by milling and grinding processes. Tests were carried out using variable displacement method where amplitude of imposed displacement was gradually increased after every 1000 cycles from 2 to 30 µm. The surfaces after tribological tests were measured by interferometric profiler. Main findings confirm that initial roughness has a significant influence on antiwear tribofilm formation in boundary lubricated contact. Tribofilm form faster and require less energy to activate in case of rough surface obtained by milling process than in case of smooth grinded surface. However, in contact lubricated by ZDDP additive a significant transfer of material occurred from plane to sphere specimen

Steric and electronic control of an ultrafast isomerization.

Synthetic control of the influence of steric and electronic factors on the ultrafast (picosecond) isomerization of penta-coordinate ruthenium dithietene complexes (Ru((CF3)2C2S2)(CO)(L)2, where L = a monodentate phosphine ligand) is reported. Seven new ruthenium dithietene complexes were prepared and characterized by single crystal X-ray diffraction. The complexes are all square pyramidal and differ only in the axial vs. equatorial coordination of the carbonyl ligand. Fourier Transform Infrared (FTIR) spectroscopy was used to study the ν(CO) bandshapes of the complexes in solution, and these reveal rapid exchange between two or three isomers of each complex. Isomerization is proposed to follow a Berry psuedorotation-like mechanism where a metastable, trigonal bipyramidal (TBP) intermediate is observed spectroscopically. Electronic tuning of the phosphine ligands L = PPh3, P((p-Me)Ph)3, ((p-Cl)Ph)3, at constant cone angle is found to have little effect on the kinetics or thermodynamic stabilities of the axial, equatorial and TBP isomers of the differently substituted complexes. Steric tuning of the phosphine ligands over a range of phosphine cone angles (135 < θ < 165°) has a profound impact on the isomerization process, and in the limit of greatest steric bulk, the axial isomer is not observable. Temperature dependence of the FTIR spectra was used to obtain the relative thermodynamic stabilities of the different isomers of each of the seven ruthenium dithietene complexes. This study details how ligand steric effects can be used to direct the solution state dynamics on the picosecond time scale of discrete isomers energetically separated by <2.2 kcal mol-1. This work provides the most detailed description to date of ultrafast isomerization in the ground states of transition metal complexes

Neutral interstellar He parameters in front of the heliosphere 1994--2007

Analysis of IBEX measurements of neutral interstellar He flux brought the inflow velocity vector different from the results of earlier analysis of observations from GAS/Ulysses. Recapitulation of results on the helium inflow direction from the past ~40 years suggested that the inflow direction may be changing with time. We reanalyze the old Ulysses data and reprocess them to increase the accuracy of the instrument pointing to investigate if the GAS observations support the hypothesis that the interstellar helium inflow direction is changing. We employ a similar analysis method as in the analysis of the IBEX data. We seek a parameter set that minimizes reduced chi-squared, using the Warsaw Test Particle Model for the interstellar He flux at Ulysses with a state of the art model of neutral He ionization in the heliosphere, and precisely reproducing the observation conditions. We also propose a supplementary method of constraining the parameters based on cross-correlations of parameters obtained from analysis of carefully selected subsets of data. We find that the ecliptic longitude and speed of interstellar He are in a very good agreement with the values reported in the original GAS analysis. We find, however, that the temperature is markedly higher. The 3-seasons optimum parameter set is lambda = 255.3, beta = 6, v = 26.0 km/s, T = 7500 K. We find no evidence that it is varying with time, but the uncertainty range is larger than originally reported. The originally-derived parameters of interstellar He from GAS are in good agreement with presently derived, except for the temperature, which seems to be appreciably higher, in good agreement with interstellar absorption line results. While the results of the present analysis are in marginal agreement with the earlier reported results from IBEX, the most likely values from the two analyses differ for reasons that are still not understood.Comment: submitted for publication in Astronomy & Astrophysic

Effects of electron transfer on the stability of hydrogen bonds.

The measurement of the dimerization constants of hydrogen-bonded ruthenium complexes (12, 22, 32) linked by a self-complementary pair of 4-pyridylcarboxylic acid ligands in different redox states is reported. Using a combination of FTIR and UV/vis/NIR spectroscopies, the dimerization constants (KD) of the isovalent, neutral states, 12, 22, 32, were found to range from 75 to 130 M-1 (ΔG0 = -2.56 to -2.88 kcal mol-1), while the dimerization constants (K2-) of the isovalent, doubly-reduced states, (12)2-, (22)2-, (32)2-, were found to range from 2000 to 2500 M-1 (ΔG0 = -4.5 to -4.63 kcal mol-1). From the aforementioned values and the comproportionation constant for the mixed-valent dimers, the dimerization constants (KMV) of the mixed-valent, hydrogen-bonded dimers, (12)-, (22)-, (32)-, were found to range from 0.5 × 106 to 1.2 × 106 M-1 (ΔG0 = -7.78 to -8.31 kcal mol-1). On average, the hydrogen-bonded, mixed-valent states are stabilized by -5.27 (0.04) kcal mol-1 relative to the isovalent, neutral, hydrogen-bonded dimers and -3.47 (0.06) kcal mol-1 relative to the isovalent, dianionic hydrogen bonded dimers. Electron exchange in the mixed valence states imparts significant stability to hydrogen bonding. This is the first quantitative measurement of the strength of hydrogen bonds in the presence and absence of electronic exchange