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Title: Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics

Abstract

Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, in this paper, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au20 beyond the Born–Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au20 cluster. Furthermore, our simulations show thatmore » the lifetime of the phonon-induced plasmon dephasing process is ~10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.« less

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
+ Show Author Affiliations
  1. Shenzhen JL Computational Science and Applied Research Institute (China)
  2. Shenzhen JL Computational Science and Applied Research Institute (China); Beijing Computational Science Research Center (China); Univ. of Bremen (Germany)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Electronic Science and Technology of China (China); Hong Kong Quantum AI Lab Limited (China)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1922787
Report Number(s):
LA-UR-22-25284
Journal ID: ISSN 0021-9606; TRN: US2312775
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 157; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; inorganic and physical chemistry; materials science; nanoclusters; plasmons; non-adiabatic molecular dynamics; chemical processes; phonons; Born-Oppenheimer approximation; surface hopping; linear response

Citation Formats

Wu, Xiaoyan, Liu, Baopi, Frauenheim, Thomas, Tretiak, Sergei, Yam, ChiYung, and Zhang, Yu. Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics. United States: N. p., 2022. Web. doi:10.1063/5.0127435.
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Wu, Xiaoyan, Liu, Baopi, Frauenheim, Thomas, Tretiak, Sergei, Yam, ChiYung, & Zhang, Yu. Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics. United States. https://doi.org/10.1063/5.0127435
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Wu, Xiaoyan, Liu, Baopi, Frauenheim, Thomas, Tretiak, Sergei, Yam, ChiYung, and Zhang, Yu. Thu . "Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics". United States. https://doi.org/10.1063/5.0127435. https://www.osti.gov/servlets/purl/1922787.
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@article{osti_1922787,
title = {Investigation of plasmon relaxation mechanisms using nonadiabatic molecular dynamics},
author = {Wu, Xiaoyan and Liu, Baopi and Frauenheim, Thomas and Tretiak, Sergei and Yam, ChiYung and Zhang, Yu},
abstractNote = {Hot carriers generated from the decay of plasmon excitation can be harvested to drive a wide range of physical or chemical processes. However, their generation efficiency is limited by the concomitant phonon-induced relaxation processes by which the energy in excited carriers is transformed into heat. However, simulations of dynamics of nanoscale clusters are challenging due to the computational complexity involved. Here, in this paper, we adopt our newly developed Trajectory Surface Hopping (TSH) nonadiabatic molecular dynamics algorithm to simulate plasmon relaxation in Au20 clusters, taking the atomistic details into account. The electronic properties are treated within the Linear Response Time-Dependent Tight-binding Density Functional Theory (LR-TDDFTB) framework. The relaxation of plasmon due to coupling to phonon modes in Au20 beyond the Born–Oppenheimer approximation is described by the TSH algorithm. The numerically efficient LR-TDDFTB method allows us to address a dense manifold of excited states to ensure the inclusion of plasmon excitation. Starting from the photoexcited plasmon states in Au20 cluster, we find that the time constant for relaxation from plasmon excited states to the lowest excited states is about 2.7 ps, mainly resulting from a stepwise decay process caused by low-frequency phonons of the Au20 cluster. Furthermore, our simulations show that the lifetime of the phonon-induced plasmon dephasing process is ~10.4 fs and that such a swift process can be attributed to the strong nonadiabatic effect in small clusters. Our simulations demonstrate a detailed description of the dynamic processes in nanoclusters, including plasmon excitation, hot carrier generation from plasmon excitation dephasing, and the subsequent phonon-induced relaxation process.},
doi = {10.1063/5.0127435},
journal = {Journal of Chemical Physics},
number = 21,
volume = 157,
place = {United States},
year = {Thu Dec 01 00:00:00 EST 2022},
month = {Thu Dec 01 00:00:00 EST 2022}
}
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