Presentation Information
[3E08]Adsorption rather than spin crossover governs Al13- superatom oxidation
*Chiong Meliton1, Atsushi Nakajima2, Yoshitada Morikawa1 (1. Graduate School of Engineering, The University of Osaka (Japan), 2. Graduate School of Science, Keio University (Japan))
The oxidation resistance of the Al13- superatom has traditionally been attributed to a spin-crossover bottleneck during O2 adsorption. Using diffusion Monte Carlo (DMC), we directly compare the O2 adsorption barrier and the triplet–singlet minimum-energy crossing point. The DMC results show that the adsorption barrier is 40 meV higher than the spin-crossover barrier, indicating that adsorption is the kinetic bottleneck. In contrast, PBE density functional theory predicts barrierless adsorption because self-interaction error overstabilizes charge transfer. The oxidation mechanisms of neutral Al13 and cationic Al13+ are also investigated through spin–orbit coupling calculations, Al 2p core-level shifts, and charge-state analyses. These results provide a unified understanding of oxygen activation on aluminum superatoms and offer guidance for designing oxidation-resistant superatom-based materials.
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