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We present the first experimental investigation of the effect of increasedisotropic pressure on the superatomic electronic structure of metalnanoclusters in the molecular state. Broad multiband absorbing[Ag44(SPhCOOH)30]4-, [Ag44(SPhF2)30]4- & [Ag25(SPhMe2)18]- nanoclusters wereoptically examined up to 200 MPa, revealing a reversible change to thesuperatomic electronic structure. Deviations from the ambient spectra becamesignificant above 50 MPa, revealing both red and blue shifts to spectralfeatures. Comparison of the spectral peaks to calculated electronic transitionsindicate that electronic states on the ligand are destabilized and that thesplitting of the superatomic orbitals decreases with increasing pressure. Thesefindings highlight that under relatively modest pressure the fundamentalsuperatomic electronic structure of metal nanoclusters can be manipulated, thusthe optical and electronic properties of functional materials containingnanoclusters such as in solar cells and photocatalytic devices can be tuned bythe application of pressure.

The Effect of Isotropic Pressure on the Electronic Structure and  Superatomic Orbitals of Molecular [Ag44(SPhCOOH)30]4-, [Ag44(SPhF2)30]4- &  [Ag25(SPhMe2)18]- Nanoclusters