Real-Space Constrained Density Functional Theory Investigation of Site-Specific, Interfacial Charge Recombination Dynamics Across the Au Nanoparticle/TiO2 Heterojunction
Drew M. Glenna, Carlos Mora Perez, Ernest Hermosillo, Haiyan Zhao, Jin Qian
TL;DR
This paper uses advanced theory to study how charges recombine at the interface of gold nanoparticles and titanium dioxide, important for improving solar energy technologies.
Contribution
The study introduces a novel combination of real-space constrained DFT and Marcus theory to model interfacial charge recombination dynamics.
Findings
Charge recombination is dominated by transitions from TiO2 LUMO to Au HOMO at interfacial Au sites.
Marcus theory predictions align with surface hopping methods but differ in time scales and efficiency.
Au cluster size influences free energy and reorganization energy, affecting charge transfer trends.
Abstract
Au nanoparticle (NP)/TiO2 heterojunction is a representative system to study interfacial charge transfer in photocatalysis and photovoltaics, where suppressing recombination from TiO2 to Au can enhance hot carrier extraction. We apply real-space constrained density functional theory (CDFT) with Marcus theory to quantify charge recombination time scales across Au/TiO2. This approach enables direct control and visualization of charge-separated states, aligning with site-specific probes like time-resolved X-ray photoelectron spectroscopy (trXPS). We find that the charge-separated state features a bipolaron, with recombination dominated by TiO2 LUMO to Au HOMO transitions, primarily at interfacial Au sites. Marcus rate predictions are benchmarked with surface hopping methods, quantifying differences in time scales and computational efficiency. Lastly, we examine how the Au cluster size…
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Taxonomy
TopicsTiO2 Photocatalysis and Solar Cells · Electron and X-Ray Spectroscopy Techniques · Gold and Silver Nanoparticles Synthesis and Applications