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

Abstract

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$^{-1}$