Unique thermodynamic relationships for ΔfHo and ΔfGo for crystalline inorganic salts. I, Predicting the possible existence and synthesis of Na2SO2 and Na2SeO2

The concept that equates oxidation and pressure has been successfully utilized in explaining the structural changes observed in the M2S subnets of M2SOx (x = 3, 4) compounds (M = Na, K) when compared with the structures (room- and high-pressure phases) of their parent M2S 'alloy' [Martinez-Cruz et al. (1994), J. Solid State Chem. 110, 397-398; Vegas (2000), Crystallogr. Rev. 7, 189-286; Vegas et al. (2002), Solid State Sci. 4, 1077-1081]. These structural changes suggest that if M2SO2 would exist, its cation array might well have an anti-CaF2 structure. On the other hand, in an analysis of the existing thermodynamic data for M2S, M2SO3 and M2SO4 we have identified, and report, a series of unique linear relationships between the known Delta H-f(o) and Delta(f)G(o) values of the alkali metal (M) sulfide (x = 0) and their oxyanion salts M2SOx (x = 3 and 4), and the similarly between M2S2 disulfide (x = 0) and disulfur oxyanion salts M2S2Ox (x = 3, 4, 5, 6 and 7) and the number of O atoms in their anions x. These linear relationships appear to be unique to sulfur compounds and their inherent simplicity permits us to interpolate thermochemical data (Delta H-f(o)) for as yet unprepared compounds, M2SO (x = 1) and M2SO2 (x = 2). The excellent linearity indicates the reliability of the interpolated data. Making use of the volume-based thermodynamics, VBT [Jenkins et al. (1999), Inorg. Chem. 38, 3609-3620], the values of the absolute entropies were estimated and from them, the standard Delta S-f(o) values, and then the Delta(f)G(o) values of the salts. A tentative proposal is made for the synthesis of Na2SO2 which involves bubbling SO2 through a solution of sodium in liquid ammonia. For this attractive thermodynamic route, we estimate Delta G(o) to be approximately -500 kJ mol(-1). However, examination of the stability of Na2SO2 raises doubts and Na2SeO2 emerges as a more attractive target material. Its synthesis is likely to be easier and it is stable to disproportionation into Na2S and Na2SeO4. Like Na2SO2, this compound is predicted to have an anti-CaF2 Na2Se subnet

A Selected Ion Flow Tube Study of the Reactions of Several Cations with the Group 6B Hexafluorides SF6, SeF6, and TeF6

The first investigation of the ion chemistry of SeF$_6$ and TeF$_6$ is presented. Using a selected ion flow tube, the thermal rate coefficients and ion product distributions have been determined at 300 K for the reactions of fourteen atomic and molecular cations, namely H$_3$O$^+$, CF$_3^+$, CF$^+$, CF$_2^+$, H$_2$O$^+$, N$_2$O$^+$, O$^+$, CO$_2^+$, CO$^+$, N$^+$, N$_2^+$, Ar$^+$, F$^+$ and Ne$^+$ (in order of increasing recombination energy), with SeF$_6$ and TeF$_6$. The results are compared with those from the reactions of these ions with SF$_6$, for which the reactions with CF$^+$, CF$_2^+$, N$_2$O$^+$ and F$^+$ are reported for the first time. Several distinct processes are observed amongst the large number of reactions studied, including dissociative charge transfer, and F$^-$, F, F$_2^-$ and F$_2$ abstraction from the neutral reactant molecule to the reagent ion. The dissociative charge transfer channels are discussed in relation to vacuum ultraviolet photoelectron and threshold photoelectron-photoion coincidence spectra of XF$_6$ (X = S, Se, and Te). For reagent ions whose recombination energies lie between the first dissociative ionisation limit, XF$_6$ $\rightarrow$ XF$_5^+$ + F + e$^-$, and the onset of ionisation of the XF$_6$ molecule, the results suggest that if dissociative charge transfer occurs, it proceeds via an intimate encounter. For those reagent ions whose recombination energies are greater than the onset of ionisation, long-range electron transfer may occur depending on whether certain physical factors apply, for example non-zero Franck-Condon overlap. From the reaction kinetics, limits for the heats of formation of SeF$_4$, SeF$_5$, TeF$_4$ and TeF$_5$ at 298 K have been obtained; $\Delta_f$H$^o$(SeF$_4$) < -369 kJ mol$^{-1}$, $\Delta_f$H$^o$(SeF$_5$) < -621 kJ mol$^{-1}$, $\Delta_f$H$^o$(TeF$_4$) > -570 kJ mol$^{-1}$, and $\Delta_f$H$^o$(TeF$_5$) < -822 kJ mol$^{-1}$

Convergence of Unregularized Online Learning Algorithms

In this paper we study the convergence of online gradient descent algorithms in reproducing kernel Hilbert spaces (RKHSs) without regularization. We establish a sufficient condition and a necessary condition for the convergence of excess generalization errors in expectation. A sufficient condition for the almost sure convergence is also given. With high probability, we provide explicit convergence rates of the excess generalization errors for both averaged iterates and the last iterate, which in turn also imply convergence rates with probability one. To our best knowledge, this is the first high-probability convergence rate for the last iterate of online gradient descent algorithms without strong convexity. Without any boundedness assumptions on iterates, our results are derived by a novel use of two measures of the algorithm's one-step progress, respectively by generalization errors and by distances in RKHSs, where the variances of the involved martingales are cancelled out by the descent property of the algorithm

Report on the EU-US Workshop on Large Scientific Databases

This joint workshop was set up under the auspices of the Joint European Commission/National Science Foundation Strategy Group that met in Budapest in September 1998. The meeting derived from a joint collaboration agreement between the EC and NSF, signed by Dr. George Metakides (Director of Information Technologies for the EC) and Prof. Juris Hartmanis (Director of Computer and Information Science and Engineering at the NSF). Some themes that were identified include: digital libraries human-centered computing and virtual environments large scientific databases, and intelligent implants This report expresses the conclusions and recommendations of the Workshop on Large Scientific Databases, held in Annapolis, Maryland, USA in September 1999. The purpose of the workshop was to develop a report to the funding agencies outlining a possible solicitation to the research community, with emphasis on joint European-US work on Large Scientific Databases. Before the workshop, each participant submitted a position paper (these are available at the web site http://www.cacr.caltech.edu/euus). The results of the position papers, presentations, and group discussion are summarized in this report. There were 12 participants from Europe and 12 from the United States, and they are listed at the end of this report. The last section of this report describes possible funding mechanisms

Electrostatic instability of ring current protons beyond the plasmapause during injection events

The stability of ring current protons with an injection spectrum modeled by an m = 2 mirror distribution function was examined for typical ring current parameters. It was found that the high frequency loss cone mode can be excited at wave numbers K lambda sub Di about = to 0.1 to 0.5, at frequencies omega about = to (0.2 to 0.6) omega sub pi and with growth rates up to gamma/omega about = to 0.03. These waves interact with the main body of the proton distribution and propagate nearly perpendicular to the local magnetic field. Cold particle partial densities tend to reduce the growth rate so that the waves are quenched at or near to the plasmapause boundary. Wave e-folding lengths are comparable to 0.1 R sub e, compared to the value of about 4 R sub e found for ion cyclotron waves at the same plasma conditions

Current driven electrostatic and electromagnetic ion cyclotron instabilities

Growth rates and parameter dependences are calculated for the current driven instabilities of electrostatic (with finite-beta corrections) and electromagnetic ion cyclotron waves. For 0.25 (T sub e)/(T sub i) 2.5, ion cyclotron waves have large growth rates, while ion acoustic waves are still stable. In fusion devices, where electrostatic waves may be stable, electromagnetic ion cyclotron waves are unstable for beta sub i 0.001

Expected and realized income changes: Evidence from the Dutch socio-economic panel.

Income expectations play a central role in household decision making. In the life cycle model for example, consumption and savings decisions reflect expectations of future income. In empirical applications where direct information on expectations is not available, it is usually assumed that expectations are rational, and reflected by observed future realizations. In this paper, we analyze direct subjective information on expected changes of household income in one panel wave of Dutch families. First, we describe these data and investigate how the expectations can be explained by, among other variables, income changes in the past. Second, we combine these data with information on realized income changes in the next panel wave, and analyze the differences between expected and realized changes. We find that, on average, households underestimate their future income changes significantly. In particular, this holds for those families whose income has fallen in the past.