Increased Excited State Metallicity in Neutral Cr2OnClusters (n < 5) upon Sequential Oxidation

Jacob M. Garcia, Scott G. Sayres

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)15572-15575
Number of pages4
JournalJournal of the American Chemical Society
Issue number38
StatePublished - Sep 29 2021

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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