Kinetics of stepwise nitrogen adsorption by size-selected iron cluster cations: Evidence for size-dependent nitrogen phobia

We present a study of stepwise cryogenic N2 adsorption on size-selected Fen+ ( = 8 - 20) clusters within a hexapole collision cell held at T = 21 - 28 K. The stoichiometries of the observed adsorption limits and the kinetic fits of stepwise N2 uptake reveal cluster size dependent variations that characterize four structural regions. Exploratory DFT studies support tentative structural assignment in terms of icosahedral, hexagonal antiprismatic, and close-packed structural motifs. There are three particularly noteworthy cases, Fe13+ with a peculiar metastable adsorption limit, Fe17+ with unprecedented nitrogen phobia (inefficient N2 adsorption), and Fe18+ with an isomeric mixture that undergoes relaxation upon considerable N2 uptake.