In the present work very-high-n Rydberg-atoms
(nsim100−nsim400) are used to probe electron-molecule collisions at ultra-low electron energies. Based on the essentially-free-electron model, for sufficiently high n, Rydberg atom-molecule collisions can be described in terms of a binary interaction between the target molecule and the essentially-free Rydberg electron. Since the average kinetic energy of the Rydberg electron is ultra-low
rm(sim85mueV−sim1.4meV), analysis of the very-high-n Rydberg-atom collision data can provide information on electron-molecule scattering at electron energies corresponding to electron temperatures of only $\\sim
1\\sp\\circ$K, which are far below those accessible using any alternate approach.\nRate constants for destruction of very-high-n Rydberg atoms in collisions with various target molecules have been measured. This study focuses on Rydberg electron transfer to an electron-attaching molecule which results in negative ion formation via the reactions
rmK(itnp/)+XYtoKsp++(XY)sp−∗ortoKsp++Xsp−+Yeqno(1)and on rotational energy transfer from polar molecules which leads to Rydberg atom ionization
rmK(itnp/)+XY(itJ/)toKsp++itesp−+XY(itJ/−1)eqno(2)\nThe n dependence of the rate constants for Rydberg-atom destruction depends on the reactions involved. In reaction (1) the rate constant is independent of n whereas in reaction (2) it increases nearly linearly with n. When both reactions are possible, the measured n dependence can be explained in terms of contributions from each process.\nThe essentially-free-electron model suggests that the n dependence of the rate constants for Rydberg-atom destruction reflects the energy dependence of the cross sections of the corresponding free electron-molecule collision processes which are $$\\eqalignno{&e\\sp- + \\rm XY \\to (XY)\\sp{-*}\\ or\\ \\to X\\sp- + Y&(1\\sp\\prime)\\cr &e\\sp- + \\rm XY({\\it J\\/}) \\to {\\it e}\\sp- + XY({\\it J\\/}-1)&(2\\sp\\prime)\\cr}$$Analysis of the data therefore provides the behavior of cross sections for these processes at ultra-low electron energies.