Cross-section energy dependence of the [C6H6–M]+ adduct formation between benzene molecules and alkali ions (M = Li, Na, K)

Abstract

The association reactions of benzene molecules with alkali ions M⁺ (Li⁺, Na⁺ and K⁺) under single collision conditions have been studied using a radiofrequency-guided-ion-beam apparatus and mass spectrometry characterization of the different adducts. Cross-section energy dependences for [M–C₆H₆]⁺ adduct formation have been measured at collision energies up to 1.20 eV in the center of mass frame. All excitation functions decrease when collision energy increases, showing the expected behaviour for barrierless reactions. From ab initio chemical structure calculations at the MP2(full) level, the formation of the adducts makes evident the alkali ion–benzene non-covalent chemical bond. The cross-section energy dependence and the role of radiative cooling rates and unimolecular decomposition on the stabilization of the energized collision complex are also discussed.