Frustrated charge transfer in vibrationally inelastic Ar++N2 collisions via hard collision glory scattering

Vibrational energy transfer in collisions between ions and neutrals is a fundamental process in interstellar media, planetary atmospheres, and plasmas. The conventional wisdom is that glancing collisions with large impact parameters are forward-scattered with low vibrational excitation, while hard collisions with small impact parameters are sideway- or backward-scattered with relatively high vibrational excitation. Here, we report experimental observations with a three-dimensional velocity-map imaging crossed-beam apparatus in the inelastic scattering process Ar⁺+N₂(v′′ = 0, J′′)→Ar⁺+N₂(v′, J′), where all the vibrationally excited N₂ products are dominated by forward scattering, contradicting the textbook model. Trajectory surface hopping calculations not only reproduced the experimental observation qualitatively, but also revealed that the vibrational excitation mainly occurs through a transient charge-transfer process. The hard collision glory mechanism, which has so far only been observed in inelastic rotational energy transfer between neutrals, is shown to play a major role for vibrational excitation in the inelastic Ar⁺+N₂ collision, via the frustrated charge transfer process.