Light-Induced Charge Transfer from Transition-Metal-Doped Aluminum Clusters to Carbon Dioxide

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 125; no. 27; pp. 5878 - 5885
• Main Authors: Göbel, Alexandra, Rubio, Angel, Lischner, Johannes
• Format: Journal Article
• Language: English
• Published: American Chemical Society 15.07.2021
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c02621

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.