Plasmonic Hot-Carrier Mediated Tunable Photochemical Reactions

Yu Zhang, Tammie R. Nelson, Sergei Tretiak, Hua Guo, George C Schatz

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Hot-carrier generation from surface plasmon decay has found applications in many branches of physics, chemistry, materials science, and energy science. Recent reports demonstrated that the hot-carriers generated from plasmon decay in nanoparticles can transfer to attached molecules and drive photochemistry which was thought impossible previously. In this work, we have computationally explored the atomic-scale mechanism of a plasmonic hot-carrier mediated chemical process, H$-2$ dissociation. Numerical simulations demonstrate that, after photoexcitation, hot-carriers transfer to the antibonding state of the H$-2$ molecule from the nanoparticle, resulting in a repulsive potential energy surface and H$-2$ dissociation. This process occurs when the molecule is close to a single nanoparticle. However, if the molecule is located at the center of the gap in a plasmonic dimer, dissociation is suppressed due to sequential charge transfer which efficiently reduces occupation in the anti-bonding state, which in turn reduces dissociation. An asymmetric displacement of the molecule in the gap breaks the symmetry, and restores dissociation when the additional charge transfer is significantly suppressed. Thus, these models demonstrate the possibility of structurally tunable photochemistry via plasmonic hot-carriers.

Original languageEnglish
JournalACS Nano
DOIs
Publication statusAccepted/In press - May 21 2018

Fingerprint

Hot carriers
Photochemical reactions
photochemical reactions
dissociation
Molecules
molecules
Nanoparticles
nanoparticles
Charge transfer
charge transfer
Potential energy surfaces
Photoexcitation
decay
Materials science
materials science
photoexcitation
Dimers
occupation
Physics
potential energy

ASJC Scopus subject areas

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Cite this

Plasmonic Hot-Carrier Mediated Tunable Photochemical Reactions. / Zhang, Yu; Nelson, Tammie R.; Tretiak, Sergei; Guo, Hua; Schatz, George C.

In: ACS Nano, 21.05.2018.

Research output: Contribution to journalArticle

Zhang, Yu ; Nelson, Tammie R. ; Tretiak, Sergei ; Guo, Hua ; Schatz, George C. / Plasmonic Hot-Carrier Mediated Tunable Photochemical Reactions. In: ACS Nano. 2018.
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