Plasmonic Hot-Carrier-Mediated Tunable Photochemical Reactions
[1];
[2];
[2];
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[4]
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
- Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
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. Here, we have computationally explored the atomic-scale mechanism of a plasmonic hot-carrier-mediated chemical process, H2 dissociation. Numerical simulations demonstrate that, after photoexcitation, hot carriers transfer to the antibonding state of the H2 molecule from the nanoparticle, resulting in a repulsive-potential-energy surface and H2 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 antibonding state and, 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. Furthermore, these models demonstrate the possibility of structurally tunable photochemistry via plasmonic hot carriers.
- Research Organization:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); US Air Force Office of Scientific Research (AFOSR)
- Grant/Contract Number:
- AC52-06NA25396; FG02-10ER16153; FA9550-15-1-0305
- OSTI ID:
- 1461402
- Report Number(s):
- LA-UR-18-24121
- Journal Information:
- ACS Nano, Vol. 12, Issue 8; ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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