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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. 

Abstract Incorporating fluorescent quantum defects in the sidewalls of semiconducting single-wall carbon nanotubes (SWCNTs) through chemical reaction is an emerging route to predictably modify nanotube electronic structures and develop advanced photonic functionality. Applications such as room-temperature single-photon emission and high-contrast bio-imaging have been advanced through aryl-functionalized SWCNTs, in which the binding configurations of the aryl group define the energies of the emitting states. However, the chemistry of binding with atomic precision at the single-bond level and tunable control over the binding configurations are yet to be achieved. Here, we explore recently reported photosynthetic protocol and find that it can control chemical binding configurations of quantum defects, which are often referred to as organic color centers, through the spin multiplicity of photoexcited intermediates. Specifically, photoexcited aromatics react with SWCNT sidewalls to undergo a singlet-state pathway in the presence of dissolved oxygen, leading to ortho binding configurations of the aryl group on the nanotube. In contrast, the oxygen-free photoreaction activates previously inaccessible para configurations through a triplet-state mechanism. These experimental results are corroborated by first principles simulations. Such spin-selective photochemistry diversifies SWCNT emission tunability by controlling the morphology of the emitting sites. 

Semiconducting conjugated polymers (CPs) have shown great potential in organic solar cells and organic field-effect transistors (OFETs), due to their tunable electronic and optical properties. In this study, we compare computational predictions of electronic and optical properties of ensembles of cis-polyacetylene (cis-PA) multiple oligomers in two different forms (a) undoped cis-PA and (b) cis- PA doped by phosphorous fluoride (PF6−) via density functional theory (DFT) with hybrid functionals. The comparison of undoped cis-PA under the constraint of injected charge carrier and cis-PA doped by PF6− shows that either doping or injection provides very similar features in electronic structure and optical properties. Doped and injected are similar to each other and different from the pristine, undoped PA. Computed results also indicate that the injection of charge carriers and adding p-type doping into the semiconducting CP model both greatly affect the conductivity. These observations provide a better understanding and practical use of the properties of polyacetylene films for flexible electronic applications.