Light Induced Charge Transfer from Transition-metal Doped Aluminium Clusters to Carbon Dioxide

Abstract

Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photo-chemical catalytic processes. In this paper, we study light-induced electron transfer between transition metal doped aluminium clusters and CO${}_2$ 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 CO${}_2$ adsorption and light-induced electron transfer into the CO${}_2$. In all other systems, we observe ground state electron transfer into the CO${}_2$ resulting in strong adsorption and predominantly light-induced electron back-transfer from the CO${}_2$ into the cluster. These findings pave the way towards a rational design of atomically precise aluminium photo-catalysts.

References in corpus (2)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Self-consistent DFT+U method for real-space time-dependent density functional theory calculations