Electron Transfer from Highly Excited Atoms to Molecules

It is theoretically shown that the rate constant for reaction of electron transfer from highly excited atoms A ** to polyatomic molecules B, {aligned} A**+B{→}A⁺+B⁻, (1) {aligned} at thermal velocities is equal to that of non-dissociative thermal electron capture by the molecules B, {aligned} e+B{→}B⁻, (2) {aligned} based on the assumption that the negative ion formed in reaction (1) is the same species as that formed in reaction (2). The result obtained is in reasonable agreement with experimental data for reaction (1) between Ar and SF 6 . From both the present study of reaction (1) and the previous work on the ionization of the highly excited atoms by collision with polar molecules (M. Matsuzawa; J. chem. Phys. 55 (1971) 2685), it can be concluded that knowledge of inelastic scattering of a slow electron by molecules is very useful for the understanding of some kind of reactions of the highly excited atoms with these molecules.