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Metal clusters with 10 to 100 atoms supported by a solid surface show electronic structure typical of molecules and require ab initio treatments starting from their atomic structure, and they also can display collective electronic phenomena similar to plasmons in metal solids. We have employed ab initio electronic structure results from two different density functionals (PBE and the hybrid HSE06) and a reduced density matrix treatment of the dissipative photodynamics to calculate light absorbance by the large Ag clusters Ag N , N = 33, 37(open shell) and N = 32, 34 (closed shell), adsorbed at the Si(111) surface of a slab, and forming nanostructured surfaces. Results on light absorption are quite different for the two functionals, and are presented here for light absorbances using orbitals and energies from the hybrid functional giving correct energy band gaps. Absorption of Ag clusters on Si increases light absorbance versus photon energy by large percentages, with peak increases found in regions of photon energies corresponding to localized plasmons. The present metal clusters are large enough to allow for modelling with continuum dielectric treatments of their medium. A mesoscopic Drude–Lorentz model is presented in a version suitable for the present structures, and provides an interpretation of our results. The calculated range of plasmon energies overlaps with the range of solar photon energies, making the present structures and properties relevant to applications to solar photoabsorption and photocatalysis.
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This content will become publicly available on March 20, 2026
Relaxation of Photoexcited Electron–Hole Pairs at Si(111) Surfaces with Adsorbed Ag Monolayered Clusters of Increasing Size
The efficiency of silicon solar cells is affected by the light absorption and recombination losses of photoexcited charge carries. One possible way to improve the efficiency is through the deposition of transition metal nanoparticles on Si surfaces. Here, we first carry out density functional theory (DFT) calculations to obtain electronic structures for Agn (n = 1–7) monolayered clusters adsorbed on Si(111)/H surfaces. Results are presented in the form of the density of states, band gaps, and light absorption, which allow for the investigation of the interaction of Ag clusters with Si. Different behaviors can be expected depending on the size of the deposited Ag clusters. Overall, the deposition of Ag clusters leads to smaller band gaps, red-shifts, and large increases in light absorption compared to the pristine Si slab. We then study the relaxation dynamics of electron–hole pairs for slabs based on nonadiabatic couplings using the reduced density matrix approach within the Redfield formalism. Nonradiative relaxation rates are noticeably different for various structures and transitions. One observes higher relaxation rates for surfaces with adsorbates than for the pristine Si surface due to charge transfer events involving Ag orbitals. We also compute emission spectra from excited-state relaxation dynamics. The band gap emission is dark for the pristine Si due to the indirect nature of its band gap. The addition of larger Ag clusters breaks the symmetry of Si slabs, enabling indirect gap transitions. These slabs thus exhibit bright band gap emission. The introduction of adsorbates is advantageous for applications in photovoltaics and photocatalysis.
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- Award ID(s):
- 1944921
- PAR ID:
- 10612162
- Publisher / Repository:
- American chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry Letters
- Volume:
- 16
- Issue:
- 11
- ISSN:
- 1948-7185
- Page Range / eLocation ID:
- 2905 to 2913
- Subject(s) / Keyword(s):
- Adsorption Electrical Conductivity Metal Clusters Silicon Silver
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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