Nonadiabatic Effects in the Molecular Oxidation of
Subnanometric Cu5 Clusters
Posted on 2021-10-11 - 18:38
The electronic structure
of subnanometric clusters, far off the
bulk regime, is still dominated by molecular characteristics. The
spatial arrangement of the notoriously undercoordinated metal atoms
is strongly coupled to the electronic properties of the system, which
makes this class of materials particularly interesting for applications
including luminescence, sensing, bioimaging, theranostics, energy
conversion, catalysis, and photocatalysis. Opposing a common rule
of thumb that assumes an increasing chemical reactivity with smaller
cluster size, Cu5 clusters have proven to be exceptionally
resistant to irreversible oxidation, i.e., the dissociative chemisorption
of molecular oxygen. Besides providing reasons for this behavior in
the case of heavy loading with molecular oxygen, we investigate the
competition between physisorption and molecular chemisorption from
the perspective of nonadiabatic effects. Landau–Zener theory
is applied to the Cu5(O2)3 complex
to estimate the probability for a switching between the electronic
states correlating the neutral O2 + Cu5(O2)2 and the ionic O2– + (Cu5(O2)2)+ fragments in a diabatic representation.
Our work demonstrates the involvement of strong nonadiabatic effects
in the associated charge transfer process, which might be a common
motive in reactions involving subnanometric metal structures.
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Mitrushchenkov, Alexander
O.; Zanchet, Alexandre; Hauser, Andreas W.; de Lara-Castells, María Pilar (2021). Nonadiabatic Effects in the Molecular Oxidation of
Subnanometric Cu5 Clusters. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.1c07271
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AUTHORS (4)
AM
Alexander
O. Mitrushchenkov
AZ
Alexandre Zanchet
AH
Andreas W. Hauser
Md
María Pilar de Lara-Castells
KEYWORDS
smaller cluster sizematerials particularly interestingincreasing chemical reactivitybesides providing reasonsapplications including luminescence5 sub3 sub2 subelectronic states correlatingstrong nonadiabatic effectsnonadiabatic effectselectronic structureelectronic propertieswork demonstratesstrongly coupledstill dominatedspatial arrangementmolecular oxygenmolecular oxidationmolecular chemisorptionmolecular characteristicsirreversible oxidationheavy loadingexceptionally resistantenergy conversione .,dissociative chemisorptiondiabatic representationcommon rulecommon motivebulk regime