Relative anion abundances 4.6 ms after the addition of 2.6 × 10−9 cm−3 CF3Br to the afterglow as a function of the initial electron density at 400 K and 1.33 Torr. Solid lines are best-fit calculated abundances (see text); dashed lines (shown only for F−) are calculated abundances at the uncertainty limits of k F-.
Projections of the weighted least-squares goodness-of-fit of calculated to experimental anion abundances (see text), for the data shown in Fig. 1, on to three parameters (k tot, , ) for which results are reported in this work.
Rate constants for total electron attachment to CF3, k tot, (full circles) and the competing dissociative, , (open circles) and non-dissociative, , (open squares) product channels at T = 300 K. Some data points are slightly offset horizontally for clarity. Experimental data (symbols) and kinetic modeling (lines) are compared with modeled k at , corresponding to primary attachment.
Rate constants for total electron attachment to CF3, k tot = + (full circles), and the competing dissociative (open circles), and non-dissociative, (open squares), product channels at T = 300 K. Some data points are slightly offset horizontally for clarity. Experimental data (symbols) and kinetic modeling (lines) are compared with modeled k at , corresponding to primary attachment.
As Fig. 4, but for T = 600 K.
Modeled specific rate constants k det (E) for electron detachment from CF3 −* (barrier-determining modes ν = 503 cm−1: left curve; 691 cm−1: middle curve; 1224 cm−1: right curve; see text).
Modeled specific rate constants k dis (E) for dissociation of CF3 −* to F− + CF2 (looseness parameter c loose = 100 cm−1: lower curve; c loose = 1000 cm−1: middle curve; c loose = ∞(PST): upper curve; see text).
Modeled distribution functions g(E,T) of the internal energy E of CF3 −* generated by thermal electron attachment to CF3 (full lines) in comparison to thermal energy distributions of CF3 (dashed lines) (with P IVR from Eq. (15) and the other parameters corresponding to the fit to the experiments shown in Figs. 3–5, see text, full lines shifted upward for clarity).
Modeled primary attachment rate constants k at for T gas = Tel (PIVR from Eq. (13) with = 67 cm−1: full line; P IVR from Eq. (15) with = 33 cm−1; dashed line; the other parameters correspond to the fit to the experiments shown in Figs. 3–5).
As Fig. 9, but with fixed gas temperature T gas = 300 K and variable electron temperature T el .
Modeled branching fractions (dashed lines), (dotted lines), and Y tot = + (full lines) as a function of the bath gas (He) pressure and the temperature T = T gas = T el .
Measured rate constants (with high and low uncertainty limits in parentheses) along with modeled rate constants (values behind the slash).
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