LAUSR

Abstract Electrons trapped in ionic crystal defects form color centers (F-centers) important in surface science, catalysis, and optoelectronic devices. We apply the electron delocalization range function (EDR) to quantify the delocalization of surface and bulk F-centers. The EDR uses computed one-particle density matrices to quantify “delocalization lengths” capturing the characteristic size of orbital lobes. Ab initio cluster model calculations confirm that the delocalization lengths of bulk alkali halide F-centers scale with the size of the anion vacancy. Calculations on magnesium oxide surface Fs and F s + centers, as well as other anionic surface defects, show how the trapped electrons' delocalization depends on the defect morphology, defect occupancy, and the approximate treatment of electron correlation. Application to N2 activation by anionic surface defects illustrate how the trapped electron localizes into the adsorbed molecule's unoccupied orbitals. The results confirm that the EDR provides a useful tool for understanding the chemistry of surface- and bulk-trapped electrons.