Formation and stabilization of C6− by radiative electron attachment

Radiative electron attachment (REA) plays an important role in forming molecular anions in various astrophysical environments. In this work, we determined the rate coefficient for the formation of C6− by REA based on a detailed balance approach. C6− ions are stored in an electrostatic ion beam trap and are photoexcited above their adiabatic detachment energy (4.18 eV). Due to fast internal conversion and intramolecular vibrational redistribution, photoexcitation leads to the formation of temporary negative ions (TNIs), the same as those one formed by the electron attachment. Absolute vibrational autodetachment and recurrent (or Poincaré) fluorescence (RF) rate coefficients have already been reported [V. Chandrasekaran et al., J. Phys. Chem. Lett. 5, 4078 (2014)]. Knowing the branching ratios of the various competing rate coefficients is decisive to the understanding of the formation probability of anions via REA. The radiative stabilization rate of C6−, shown to be dominated by RF, was determined to be 5 × 10⁴ s⁻¹ at the electron detachment energy, i.e., at least a factor of 100 faster than the stabilization by infrared transitions. The RF is found to very effectively stabilize the TNI formed by electron attachment. Using detailed balance to link the measured delayed detachment rate to the rate of electron attachment, we estimate the REA rate leading to the formation of C6− to be 3 × 10⁻⁷ cm³ s−1 at 300 K in agreement with theory (1.7 × 10⁻⁷ cm³ s−1 [R. Terzieva and E. Herbst, Int. J. Mass Spectrom. 201, 135 (2000)]). Such a high rate for REA to C₆ indicates that REA may play a prominent role in the formation of anions in the interstellar medium.