We present an approach to master the well-known challenge of calculating the contribution of d-bands to plasmon-induced hot carrier rates in metallic nanoparticles. We generalize the widely used spherical well model for the nanoparticle wavefunctions to flat d-bands using the envelope function technique. Using Fermi’s golden rule, we calculate the generation rates of hot carriers after the decay of the plasmon due to transitions either from a d-band state to an sp-band state or from an sp-band state to another sp-band state. We apply this formalism to spherical silver nanoparticles with radii up to 20 nm and also study the dependence of hot carrier rates on the energy of the d-bands. We find that for nanoparticles with a radius less than 2.5 nm, sp-band state to sp-band state transitions dominate hot carrier production, while d-band state to sp-band state transitions give the largest contribution for larger nanoparticles.
Generation of plasmonic hot carriers from d-bands in metallic nanoparticles
Lara Román Castellanos, Juhan Matthias Kahk, Ortwin Hess, Johannes Lischner; Generation of plasmonic hot carriers from d-bands in metallic nanoparticles. J. Chem. Phys. 14 March 2020; 152 (10): 104111. https://doi.org/10.1063/5.0003123
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