Rate constants have been measured from 300 to 700 K for thermal electron attachment to F2 using two flowing afterglow–Langmuir probe apparatuses. Dissociative attachment yielding F− is observed with a rate constant of 5.0 ± 1.3 × 10−9 cm3 s−1 at 300 K, rising to 9.6 ± 2.4 × 10−9 cm3 s−1 at 700 K, well below the previously accepted values of McCorkle et al. [D. L.McCorkle, L. G. Christophorou, A. A. Christodoulides, and L. Pichiarella, J. Chem. Phys. 85, 1966 (1986)]. The absolute concentration of F2 reaching the afterglowis verified by measuring the near-collisional rate constant (4.5 ± 1.5 × 10−10 cm3 s−1) for Ar+ + F2→ArF+ + F. Prior attempts to apply R-matrix calculations to the F2 + e− system have failed to explain previously reported thermal and nonthermal attachment rate constants along with high-resolution, low-energy attachment cross sections. The present results are reproduced exceptionally well by R-matrix calculations employing previously calculated resonance widths without adjustment
