General discussion [Experiments on ion-pair formation in gas-phase polyatomic molecules]

A brief summary of experiments on ion-pair formation in gas-phase polyatomic molecules

CF3SF5 : a ‘super’ greenhouse gas

One molecule of the anthropogenic pollutant trifluoromethyl sulphur pentafluoride (CF$_3$SF$_5$), an adduct of the CF$_3$ and SF$_5$ free radicals, causes more global warming than one molecule of any other greenhouse gas yet detected in the Earth’s atmosphere. That is, it has the highest per molecule radiative forcing of any greenhouse pollutant, and the value of its global warming potential is only exceeded by that of SF$_6$. First, the greenhouse effect is described, the properties of a molecule that cause it to be a significant greenhouse gas, and therefore the contributions that physical chemistry can make to an improved understanding of the effect. Second, the chemistry of (CF$_3$SF$_5$), first discovered in the atmosphere in 2000, is taken as a case study. Experiments using tunable vacuum-UV radiation, electrons and small cations have determined some of the relevant physical properties of this molecule, including the strength of the (CF$_3$-SF$_5$) covalent bond. The main sink route to remove (CF$_3$SF$_5$) from the earth’s atmosphere is low-energy electron attachment in the mesosphere. Third, it is shown how such data are important inputs to determine the lifetime of this pollutant, ca. 1000 years, in the atmosphere. Finally, the generic lessons that can be learnt from the study of such long-lived greenhouse gases are described

Vacuum-UV negative photoion spectroscopy of gas-phase polyatomic molecules

This Review describes recent experiments to detect anions following vacuum-UV photoexcitation of gas-phase polyatomic molecules. Using synchrotron radiation in the range 10-35 eV at a resolution down to 0.02 eV, negative ions formed are detected by mass spectrometry. The molecules studied in detail include CF$_4$, SF$_6$ and CH$_4$; the CF$_3$X series where X = Cl,Br,I; the CH$_3$Y series where Y = F,Cl,Br; and SF$_5$Z where Z = CF$_3$,Cl. Spectra and raw data only are reported for other members of the CH$_x$F$_y$, CH$_x$Cl$_y$ including CCl$_4$, and CF$_x$Cl$_y$ series where ($x$+$y$) = 4; and saturated and unsaturated members of the C$_m$H$_n$ and C$_m$F$_n$ series up to m = 3. Anions detected range from atomic species such as H-, F- and Cl- through to heavier polyatomics such as SF$_5^-$, CF$_3^-$ and CH$_2$Cl$^-$. The majority of anions display a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation, generically written as ABC + h$v$ $\rightarrow$ D$^-$ + E$^+$ + neutral(s). In a few cases, the anion signal increases much more rapidly than a linear dependence with pressure, suggesting that anions now form via a multi-step process such as dissociative electron attachment. Cross sections for ion-pair formation can be put on to an absolute scale by calibrating the signal strength with those of F$^-$ from SF$_6$ and CF$_4$, although there are difficulties associated with the determination of H$^-$ cross sections from hydrogen-containing molecules unless this anion is dominant. Following normalisation to total vacuum-UV absorption cross sections (where data are available), quantum yields for anion production are obtained. Cross sections in the range ca. 10$^{-23}$ to 10$^{-19}$ cm$^2$ , and quantum yields in the range ca. 10$^{-6}$ to 10$^{-3}$ are reported. The Review describes the two ion-pair mechanisms of indirect and direct formation and their differing characteristics, and the properties needed for anion formation by dissociative electron attachment. From this huge quantity of data, attempts are made to rationalise the circumstances needed for favourable formation of anions, and which anions have the largest cross section for their formation. Since most anions form indirectly via predissociation of an initially-excited Rydberg state of the parent molecule by an ion-pair continuum, it appears that the dynamics of this curve crossing is the dominant process which determines which anions are formed preferentially. The thermochemistry of the different exit channels and the microscopic properties of the anion formed do not appear to be especially significant. Finally, for the reaction ABC + h$v$ $\rightarrow$ A$^-$ + BC$^+$ , the appearance energy of A$^-$ can be used to determine an upper limit to the bond dissociation energy of AB (to A + BC), or an upper limit to that of ABC$^+$ (to A + BC$^+$). Where known, the data are in excellent agreement with literature values

Vacuum-Ultraviolet negative photoion spectroscopy of SF5Cl

Using vacuum-UV radiation from a synchrotron, gas-phase negative ions are detected by mass spectrometry following photoexcitation of SF$_5$Cl. F$^-$, Cl$^-$ and SF$_5^-$are observed, and their ion yields recorded in the range 8-30 eV. F$^-$ and Cl$^-$ show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation, generically written AB + h$v$ $\rightarrow$ C$^-$ + D$^+$ (+ neutral(s)). F$^-$ is the strongest signal, and absolute cross sections are determined by calibrating the signal intensity with that of F$^-$ from SF$_6$ and CF$_4$. Resonances are observed, and assigned to transitions to Rydberg states of SF$_5$Cl. The Cl$^-$ signal is much weaker, despite the S-Cl bond being significantly weaker than the S-F bond. Appearance energies for F$^-$ and Cl$^-$ of 12.7 ± 0.2 and 10.6 ± 0.2 eV are determined. The spectra suggest that these ions form indirectly by crossing of Rydberg states of SF$_5$Cl onto an ion-pair continuum

Dissociation dynamics of fluorinated ethene cations:\ud from time bombs on a molecular level to double-regime dissociators\ud

The dissociative photoionization mechanism of internal energy selected C$_2$H$_3$F$^+$, 1,1-C$_2$H$_2$F$_2^+$, C$_2$HF$_3^+$ and C$_2$F$_4^+$ cations have been studied in the 13−20 eV photon energy range using imaging photoelectron photoion coincidence spectroscopy. Five predominant channels have been found; HF loss, statistical and non-statistical F loss, cleavage of the C–C bond post H or F-atom migration, and cleavage of the C=C bond. By modelling the breakdown diagrams and ion time-of-flight distributions using statistical theory, experimental 0 K appearance energies, E$_0$, of the daughter ions have been determined. Both C$_2$H$_3$F$^+$ and 1,1-C$_2$H$_2$F$_2^+$ are veritable time bombs with respect to dissociation via HF loss, where slow dissociation over a reverse barrier is followed by an explosion with large kinetic energy release. The first dissociative ionization pathway for C$_2$HF$_3$ and C$_2$F$_4$ involves an atom migration across the C=C bond, giving CF–CHF$_2^+$ and CF–CF$_3^+$, respectively, which then dissociate to form CHF$_2^+$ and CF$_3^+$. The nature of the F-loss pathway has been found to be bimodal for C$_2$H$_3$F and 1,1-C$_2$H$_2$F$_2$, switching from statistical to non-statistical behaviour as the photon energy increases. The dissociative ionization of C$_2$F$_4$ is found to be comprised of two regimes. At high internal energies, a long-lived excited electronic state is formed, which loses an F atom in a non-statistical process and undergoes statistical redistribution of energy among the nuclear degrees of freedom. This is followed by a subsequent dissociation. In other words only the ground electronic state phase space stays inaccessible. The accurate E$_0$ of CF$_3^+$ and CF$^+$ formation from C$_2$F$_4$ together with the now well established ∆$_f$Hº of C$_2$F$_4$ yield self-consistent enthalpies of formation for the CF$_3$, CF, CF$_3^+$, and CF$^+$ species

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$^{-1}$

Isomeric effects in the gas-phase reactions of dichloroethene, C2H2Cl2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH$_4^+$, H$_3$O$^+$, SF$_3^+$, CF$_3^+$, CF$^+$, SF5$^+$, SF$_2^+$, SF$^+$, CF$_2^+$, SF$_4^+$, O$_2^+$, Xe$^+$, N$_2$O$^+$, CO$_2^+$, Kr$^+$, CO$^+$, N$^+$, N$_2^+$, Ar$^+$, F$^+$ and Ne$^+$) with the three structural isomers of dichloroethene, i.e. 1,1-C$_2$H$_2$Cl$_2$, cis-1,2-C$_2$H$_2$Cl$_2$ and trans-1,2-C$_2$H$_2$Cl$_2$ is reported. The recombination energy of these ions spans the range 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube. Collisional rate coefficients are calculated by modified average dipole orientation theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C$_2$H$_2$Cl$_2$ with photon energies in the range 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H$_3$O$^+$, CF$_3^+$, and CF$^+$. For 1,1-C$_2$H$_2$Cl$_2$ the reaction with H$_3$O$^+$ proceeds at the collisional rate with the only ionic product being 1,1-C$_2$H$_2$Cl$_2$H$^+$. However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C$_2$H$_2$Cl$_2$, but only proceeds with 14 % and 18 % efficiency, respectively. The CF$_3^+$ reaction proceeds with 56-80 % efficiency, the only ionic product for 1,1-C$_2$H$_2$Cl$_2$ being C$_2$H$_2$Cl$^+$ formed via Cl- abstraction, whereas the only ionic product for both 1,2-isomers is CHCl$_2^+$ corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C$_2$H$_2$Cl$_2$ isomers, have been found in the reactions of SF$^+$, CO$_2^+$, CO$^+$, N$_2^+$, and Ar$^+$. Although these five ions have recombination energies above the ionization energy of any of the C$_2$H$_2$Cl$_2$ isomers and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C$_2$H$_2$Cl$_2$ is responsible for the observed effects

Two studies in gas-phase ion spectroscopy

The research involves two aspects of the spectroscopy and reaction kinetics of gas-phase ions. First, the observation and analysis of negative ions following vacuum-ultraviolet excitation of polyatomic molecules using tunable radiation from a synchrotron source. Second, the determination of rate coefficients and branching ratios of either cations or anions reacting with polyatomic molecules in a Selected Ion Flow Tube at 298 K

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Rate constants have been determined for the reactions of OH radicals and Cl atoms with the three partially halogenated methyl-ethyl ethers, CF$_3$CH$_2$OCHF$_2$, CF$_3$CHClOCHF$_2$ and CF$_3$CH$_2$OCClF$_2$, using discharge-flow techniques to generate the OH radicals and the Cl atoms and resonance fluorescence to observe changes in their relative concentrations in the presence of added ether. For each combination of radical and ether, experiments were carried out at three temperatures between 292 and 410 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature: OH + CF$_3$CH$_2$OCHF$_2$: $k$ = (2.0$\pm$0.8) $\times$ 10$^{-11}$ exp( – 2110 $\pm$ 150 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CHClOCHF$_2$: $k$ = (4.5 $\pm$ 1.3) $\times$ 10$^{-13}$ exp( – 940 $\pm$ 100 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CH$_2$OCClF$_2$: $k$ = (1.6 $\pm$ 0.6) $\times$ 10$^{-12}$ exp( – 1100 $\pm$ 125 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCHF$_2$: $k$ = (6.1 $\pm$ 1.4) $\times$ 10$^{-12}$ exp( – 1830 $\pm$ 90 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CHClOCHF$_2$: $k$ = (7.8 $\pm$ 2.6) $\times$ 10$^{-11}$ exp( – 2980 $\pm$ 130 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCClF$_2$: $k$ = (2.2 $\pm$ 0.2) $\times$ 10$^{-11}$ exp( – 2700 $\pm$ 40 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ The results are compared with those obtained previously for the same and related reactions of OH radicals and Cl atoms, and the atmospheric implications of the results are considered briefly

Threshold photoelectron photoion coincidence spectroscopy and selected ion flow tube reactions of CHF3: comparison of product branching ratios

The threshold photoelectron and threshold photoelectron photoion coincidence spectra of CHF$_3$ in the range 13.5 – 24.5 eV have been recorded. Ion yields and branching ratios have been determined for the three fragments CF$_3^+$, CHF2$^+$ and CF$^+$. The mean kinetic energy releases into fragment ions involving either C-H or C-F bond cleavage have been measured, and compared with statistical and impulsive models. CHF$_3^+$ behaves in a non-statistical manner characteristic of the small-molecule limit, with the ground electronic state and low-lying excited states of CHF$_3^+$ being largely repulsive along the C-H and C-F coordinates, respectively. The rate coefficients and product ion branching ratios have been measured at 298 K in a selected ion flow tube for the reactions of CHF$_3$ with a large number of gas-phase cations whose recombination energies span the range 6.3 through 21.6 eV. A comparison between the branching ratios from the two experiments, together with an analysis of the threshold photoelectron spectrum of CHF$_3$, shows that long-range charge transfer probably occurs for the Ar$^+$ and F$^+$ atomic ions whose recombination energies lie above ca. 15 eV. Below this energy, the mechanism involves a combination of short-range charge transfer and chemical reactions involving a transition state intermediate