Time-dependent GW (TDGW) molecular dynamics simulation of nickel-atom aided photolysis of methane

Methane photolysis (CH₄ → CH₃^· + H) is key in hydrogen production for alternative energy applications. We recently demonstrated using our newly developed novel method, non-adiabatic excited-state time-dependent GW (TDGW) molecular dynamics (MD), how this process was captured accurately via the time-tracing of all quasiparticle (QP) levels [J. Chem. Phys. 160, 184102 (2024)]. However, significant photoabsorption energy (PAE ∼ 10.2 eV) is required and only one H atom is produced via single photon absorption. To lower this optical gap and facilitate efficient hydrogen production, transition metal atoms can serve as agents in photochemical reactions. In this talk, I will briefly describe the TDGW-MD method and its application to accurately capture the pristine methane photolysis dynamics. Following this, I will describe methane photolysis in the presence of a Ni atom, using TDGW-MD. In this case, H ejection can occur either towards or away from Ni. Only in the case of the H-ejection-away-from-Ni trajectory does a H₂ molecule form, with the corresponding QP level having an energy matching the ionization potential of isolated H₂. This demonstrates the dissociation of two H atoms forming a molecule via single photon absorption, at a lower PAE of 8.4 eV compared to pristine methane.