Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism
Abstract
Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au38(SC2H4Ph)24. The bi-icosahedral Au38 (denoted as Au38Q) with a Au23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au38T) exhibits similar relaxation processes, but the rapid decay is accelerated by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au13 capped by a Au12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm–1 for Au38Q, 27 and 60 cm–1 for Au38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.
- Authors:
-
[1];
[3];
[1]
- Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Chemistry
- Chinese Academy of Sciences (CAS), Beijing (China). Key Lab. of Materials Physics, Anhui Key Lab. of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1394758
- Report Number(s):
- BNL-114329-2017-JA
Journal ID: ISSN 1932-7447; KC0403020
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 20; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Center for Functional Nanomaterials
Citation Formats
Zhou, Meng, Tian, Shubo, Zeng, Chenjie, Sfeir, Matthew Y., Wu, Zhikun, and Jin, Rongchao. Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b10360.
Zhou, Meng, Tian, Shubo, Zeng, Chenjie, Sfeir, Matthew Y., Wu, Zhikun, & Jin, Rongchao. Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism. United States. https://doi.org/10.1021/acs.jpcc.6b10360
Zhou, Meng, Tian, Shubo, Zeng, Chenjie, Sfeir, Matthew Y., Wu, Zhikun, and Jin, Rongchao. Thu .
"Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism". United States. https://doi.org/10.1021/acs.jpcc.6b10360. https://www.osti.gov/servlets/purl/1394758.
@article{osti_1394758,
title = {Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism},
author = {Zhou, Meng and Tian, Shubo and Zeng, Chenjie and Sfeir, Matthew Y. and Wu, Zhikun and Jin, Rongchao},
abstractNote = {Structural isomerism in nanoparticles has recently emerged as a new topic and stimulated research interest because the atomic structures of ultrasmall nanoparticles may have great impact on their fundamental properties and applications. We report the correlation between ultrafast relaxation dynamics and atomic structures of two isomers of thiolate-protected Au38(SC2H4Ph)24. The bi-icosahedral Au38 (denoted as Au38Q) with a Au23 inner core in its atomic structure shows rapid decay (1.5 ps) followed by nanosecond relaxation to the ground state, whereas its structural isomer (Au38T) exhibits similar relaxation processes, but the rapid decay is accelerated by ~50% (1.0 ps). The picosecond relaxations in both cases can be assigned to core–shell charge transfer or electronic rearrangement within the metal core. The acceleration of the fast decay in Au38T is ascribed to its unique core structure, which is made up of a mono-icosahedral Au13 capped by a Au12 tri-tetrahedron by sharing two atoms. Interestingly, coherent phonon emissions (25 cm–1 for Au38Q, 27 and 60 cm–1 for Au38T) are observed in both isomers with pumping in the NIR region. These results illustrate for the first time the importance of atomic structures in the photophysics of same sized gold nanoclusters.},
doi = {10.1021/acs.jpcc.6b10360},
journal = {Journal of Physical Chemistry. C},
number = 20,
volume = 121,
place = {United States},
year = {Thu Dec 22 00:00:00 EST 2016},
month = {Thu Dec 22 00:00:00 EST 2016}
}
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