Year: 2026
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Photoactive nanoclusters are often assumed to exist as a single isomer corresponding to the lowest-energy local minimum structure. However, at finite temperatures, multiple configurations may be thermally accessible. Using ab initio molecular dynamics combined with time-dependent density functional theory, we identify a fluxional mode associated with low-energy structural rearrangement that can directly influence excited-state dynamics in a model titania nanocluster. This thermally driven mode reshapes the low-energy excited-state manifold, producing a broader, bimodal S 1 excitation-energy distribution. Nonadiabatic dynamics reveals two distinct consequences. Relaxation toward S 1 accelerates because fluxionality changes the energetic end point of the decay pathway, whereas ground-state recombination accelerates through enhanced sampling of strongly coupled S 0 –S 1 configurations. These findings establish local coordination fluxionality as a structural mechanism for reshaping excited-state landscapes in oxide nanoclusters, with implications for tuning nonradiative decay and charge recombination pathways in photocatalytic metal oxides.
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G1175115578, G1184413409, G121809054, G145641598, G1510469474, G1827121850, G1855990336, G1903514128, G2064873908, G2089336561, G2262748287, G2309174360, G2469010403, G2543706835, CAREER: Toward Reliable Nonadiabatic Dynamics in Condensed Matter and Nanoscale Systems, G2660406951, G2744316779, G279363373, G2907678734, G3005324705, G300979063, G34346518, G3480869486, G3518538256, G3546882995, G425668148, G430777504, G4526231891, G5080475149, G5421974903, G5959322008, G6371956759, G69051668, G7084143925, G734693063, G7434936867, G8418175817, G897484643, G919199058, G979456341, G99296377
OpenAlex ID: W7166697837