Increased Excited State Metallicity in Neutral Cr₂O_nClusters (n < 5) upon Sequential Oxidation

Excited state lifetimes of neutral Cr2On (n < 5) clusters were measured using femtosecond pump-probe spectroscopy. Density functional theory calculations reveal that the excited state dynamics are correlated with changes in the cluster's electronic structure with increasing oxidation. Upon absorption of a UV (400 nm) photon, the clusters exhibit features attributed to three separate relaxation processes. All clusters exhibit similar subpicosecond lifetimes, attributed to vibrational relaxation. However, the ∼30 fs transient signal fraction grows linearly with oxidation, matching the amount of O to Cr charge transfer character of the photoexcitation and highlighting a gradual transition between semiconducting and metallic behavior at the molecular level. A long-lived (>2.5 ps) response is recorded only in clusters with significant d-electron character, suggesting that adiabatic relaxation back to the ground state is efficient in heavily oxidized clusters, due to the presence of terminal O atoms. The simple picture of sequential oxidation of Cr2On reveals a linear variation in the contributions of each relaxation component to the total transient signals, therefore opening possibilities for the design of new molecular spintronic materials.