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Title: Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacks ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2] ;  [2] ;  [3] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Inst. for Molecular Science, Okazaki (Japan). Dept. of Theoretical and Computational Molecular Science ; Kyoto Univ. (Japan). Elements Strategy Initiative for Catalysts and Batteries (ESICB)
Publication Date:
Report Number(s):
BNL-114816-2017-JAAM
Journal ID: ISSN 1948-7185; TRN: US1801998
Grant/Contract Number:
SC0012704; FA9550-15-1-9999; FA9550-15-1-0154; 25288012
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 17; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); US Air Force Office of Scientific Research (AFOSR); Japan Society for the Promotion of Science (JSPS); Ministry of Education, Culture, Sports, Science and Technology (MEXT), Tokyo (Japan)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1425010

Zhou, Meng, Zeng, Chenjie, Sfeir, Matthew Y., Cotlet, Mircea, Iida, Kenji, Nobusada, Katsuyuki, and Jin, Rongchao. Evolution of Excited-State Dynamics in Periodic Au28, Au36, Au44, and Au52 Nanoclusters. United States: N. p., Web. doi:10.1021/acs.jpclett.7b01597.
Zhou, Meng, Zeng, Chenjie, Sfeir, Matthew Y., Cotlet, Mircea, Iida, Kenji, Nobusada, Katsuyuki, & Jin, Rongchao. Evolution of Excited-State Dynamics in Periodic Au28, Au36, Au44, and Au52 Nanoclusters. United States. doi:10.1021/acs.jpclett.7b01597.
Zhou, Meng, Zeng, Chenjie, Sfeir, Matthew Y., Cotlet, Mircea, Iida, Kenji, Nobusada, Katsuyuki, and Jin, Rongchao. 2017. "Evolution of Excited-State Dynamics in Periodic Au28, Au36, Au44, and Au52 Nanoclusters". United States. doi:10.1021/acs.jpclett.7b01597. https://www.osti.gov/servlets/purl/1425010.
@article{osti_1425010,
title = {Evolution of Excited-State Dynamics in Periodic Au28, Au36, Au44, and Au52 Nanoclusters},
author = {Zhou, Meng and Zeng, Chenjie and Sfeir, Matthew Y. and Cotlet, Mircea and Iida, Kenji and Nobusada, Katsuyuki and Jin, Rongchao},
abstractNote = {An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au28, Au36, Au44, and Au52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast Sn → S1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacks ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.},
doi = {10.1021/acs.jpclett.7b01597},
journal = {Journal of Physical Chemistry Letters},
number = 17,
volume = 8,
place = {United States},
year = {2017},
month = {8}
}