Plasmon-induced hot-carrier transfer from a metal nanostructure to an acceptor is known to occur via two key mechanisms: (i) indirect transfer, where the hot carriers are produced in the metal nanostructure and subsequently transferred to the acceptor, and (ii) direct transfer, where the plasmons decay by directly exciting carriers from the metal to the acceptor. Unfortunately, an atomic-level understanding of the direct-transfer process, especially with regard to its quantification, remains elusive even though it is estimated to be more efficient compared to the indirect-transfer process. This is due to experimental challenges in separating direct from indirect transfer as both processes occur simultaneously at femtosecond timescales. Here, we employ timedependent density-functional theory simulations to isolate and study the direct-transfer process at a model metal-acceptor (Ag 147 -Cd 33 Se 33 ) interface. Our simulations show that, for a 10-femtosecond Gaussian laser pulse tuned to the plasmon frequency, the plasmon formed in the Ag 147 -Cd 33 Se 33 system decays within 10 fs and induces the direct transfer with a probability of about 40%. We decompose the direct-transfer process further and demonstrate that the direct injection of both electrons and holes into the acceptor, termed direct hot-electron transfer (DHET) and direct hot-hole transfer (DHHT), take place with similar probabilities of about 20% each. Finally, effective strategies to control and tune the probabilities of DHET and DHHT processes are proposed. We envision our work to provide guidelines toward the design of metal-acceptor interfaces that enable more efficient plasmonic hot-carrier devices.

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artist Holderstr.4 4057 Basel 0041 (0)61 631 34 35 shauert@dplanet.ch Daniel Reichmuth artist Holderstr.4 4057 Basel 0041 (0)61 631 34 35 info@rosen-spademan.net Volker Böhm musician, programmer, audiodesigner Klybeckstr. 94 4057 Basel 0041 (0)61 683 44 09 vboehm@gmx.ch Biographical information Sibylle Hauert & Daniel ReichmuthSince 1999, Sibylle Hauert and Daniel Reichmuth work together as artists and performer in the field of new media installation and research with an educational and training background in theatre, music and electrical engineering. Since 2000, they have worked on self-built electronic systems in connection with developable creative software programs to stage and provoke real movement and sensual perception through electronic installations or performative "TOOLS". Volker BöhmBorn 1971, he studied "Audiodesign" at the Electronic Studio, Music-Academy Basel by Wolfgang Heiniger and Thomas Kessler and School Music and Music Theorie at the Music Academie Freiburg. Since 2004 he is head master of the course "Audiodesign" at the Electronic Studio, Music-Academy Basel. He lives and works as musician, programmer and audiodesigner in Basel.