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Abstract

Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photochemical catalytic processes. In this paper, we study light-induced electron transfer between transition-metal-doped aluminum clusters and CO₂ molecules using first-principles time-dependent density-functional theory. Specifically, we carry out calculations for a range of dopants (Zr, Mn, Fe, Ru, Co, Ni, and Cu) and find that the resulting systems fall into two categories: Cu- and Fe-doped clusters exhibit no ground-state charge transfer, weak CO₂ adsorption, and light-induced electron transfer into the CO₂. In all other systems, we observe ground-state electron transfer into the CO₂ resulting in strong adsorption and predominantly light-induced electron back-transfer from the CO₂ into the cluster. These findings pave the way toward a rational design of atomically precise aluminum photocatalysts.