Theory of highly charged ion energy gain spectroscopy of molecular collective excitations

This paper discusses the physical mechanism by which a highly charged, energetic ion partly neutralized by electron transfers from a target-a large molecule, a cluster or a solid surface-can create target collective excitations in the process. We develop an analysis for the system of a highly charged ion flying by a fullerene molecule. Our analysis offers a new explanation for the periodic oscillations observed in the high-resolution energy gain spectra of energetic Arq+ ions (q=8, 13, 14, 15) flying by C60 molecules. For the Arq+→Ar(q-s)+ spectra with q=13-15 and s=1 or 2, the observed oscillations of 6 eV periodicity are assigned to energy losses due to multiple, Poissonian excitations of C60 π-plasmons (6 eV quantum). The excitation energy quanta are subtracted from the kinetic energy gained by the ion when one or at most two electrons are transferred to increasingly deep Rydberg states of the ion. The observed 3 eV periodicity for q=8 arises from the specific Rydberg energy levels of ArVIII (Ar7+). The first few shallow levels of this ion are separated by about 3 eV, while some of the pairs of adjacent, deeper levels are also separated by 3 eV. Each deep-level pair produces two interdigitated, Poissonian series of 6 eV π-plasmon excitation peaks resulting in an apparent periodicity of 3 eV throughout the spectra. The broad σ-plasmons (25 eV quantum) are found to contribute a background continuum to the medium- and high-energy regions of the observed spectra. The physical model analyzed here indicates that electronic collective excitations in several other systems could be studied by highly charged ion energy gain spectroscopy at sufficient resolution.