Light-initiated generation of energetic carriers has attracted considerable attention as a paradigm for photocatalysis and solar energy conversion, and the use of noble metal nanoparticles that support localized surface plasmon resonances has been widely explored as a medium for realizing this paradigm. It was recently shown that composite nanostructures enabling the interplay between dielectric scattering resonances and broadband absorption in small metal nanostructures, a phenomenon termed scatteringmediated absorption, can be used to mediate energetic carrier transfer and selective photochemistry with low-intensity light while completely circumventing plasmon resonance. In this work, we develop a multiscale modeling approach for elucidating the hot carrier dynamics initiated by scattering-mediated absorption. Our calculations reveal that unique hot carrier distributions and dynamics arise from scattering-mediated absorption as compared to plasmon excitation and also suggest that in a variety of circumstances scattering-mediated absorption may lead to more efficient hot carrier generation compared to plasmon resonance under the same external illumination conditions. These results are an important first step in understanding the phenomena of scattering-mediated hot carrier generation, which has potential for expanding the palette of materials that can be utilized for hot carrier mediated photochemistry beyond plasmonic metals and for enabling unique pathways for photocatalytic transformations.

Nanostructure-mediated energy transfer has attracted considerable attention as a template for photocatalysis and solar energy conversion, and the use of noble metal nanoparticles that support localized surface plasmon resonances (LSPRs) has been widely explored as a medium for realizing this paradigm. On the other hand, composite nanoparticles (CNPs) comprised of a large dielectric bead and smaller metal nanostructures have been shown to achieve efficient energy transfer to small-molecule adsorbates through the interplay between dielectric scattering resonances and the broad-band absorption associated with the metal nanostructure. This scattering mediated absorption can enable selective photochemistry without relying on the plasmonic properties of noble metal nanoparticles. While the precise photochemical mechanisms themselves remain unknown, resonance energy transfer (RET) is one feasible route for initiating the photochemistry. We demonstrate computationally that CNPs indeed facilitate RET to small-molecule adsorbates and that CNPs offer a framework in which one can design RET donors that outperform typical plasmonic nanoparticles employed within LSPRdriven RET under comparable illumination conditions. We also exploit the tunability of the resonances on the CNPs to realize strong coupling between the CNP and LSPR modes.

WPTherml is a Python package for the design of materials with tailored optical and thermal properties for the vast number of energy applications where control of absorption and emission of radiation, or conversion of heat to radiation or vice versa, is paramount. The optical properties are treated within classical electrodynamics via the Transfer Matrix Method which rigorously solves Maxwell's equations for layered isotropic media. A flexible multilayer class connects rigorous electrodynamics properties to figures of merit for a variety of thermal applications, and facilitates extensions to other applications for greater reuse potential. WPTherml can be accessed at https://github.com/FoleyLab/wptherml.

<p>Nanostructure-mediated energy transfer has attracted considerable attention</p> <p>as a template for photocatalysis and solar energy conversion, and the use</p> <p>of noble metal nanoparticles that support localized surface plasmon</p> <p>resonances (LSPRs) has been widely explored as a medium for realizing</p> <p>this paradigm. On the other hand, composite nanoparticles (CNPs)</p> <p>comprised of a large dielectric bead and smaller metal nanostructures have</p> <p>been shown to achieve efficient energy transfer to small-molecule</p> <p>adsorbates through the interplay between dielectric scattering resonances</p> <p>and the broad-band absorption associated with the metal nanostructure.</p> <p>This scattering mediated absorption can enable selective photochemistry</p> <p>without relying on the plasmonic properties of noble metal nanoparticles.</p> <p>While the precise photochemical mechanisms themselves remain unknown,</p> <p>resonance energy transfer (RET) is one feasible route for initiating the</p> <p>photochemistry. We demonstrate computationally that CNPs indeed</p> <p>facilitate RET to small-molecule adsorbates and that CNPs offer a</p> <p>framework in which one can design RET donors that outperform typical</p> <p>plasmonic nanoparticles employed within LSPR-driven RET under comparable</p> <p>illumination conditions. We also exploit the tunability of the resonances</p> <p>on the CNPs to realize strong coupling between the CNP and LSPR modes.</p>

<p>WPTherml is a Python package for the design of materials with tailored optical and thermal properties for the vast number of energy applications where control of absorption and emission of radiation, or conversion of heat to radiation or vice versa, is paramount. The optical properties are treated within classical electrodynamics via the Transfer Matrix Method which rigorously solve Maxwell's equations for layered isotropic media. A flexible multilayer class connects rigorous electrodynamics properties to figures of merit for a variety of thermal applications, and facilitates extensions to other applications for greater reuse potential. WPTherml can be accessed at https://github.com/FoleyLab/wptherml. </p>