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Title: Electron localization in rod-shaped triicosahedral gold nanocluster

Abstract

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons to one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm-1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensionalmore » gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.« less

Authors:
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Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
US Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1360862
Alternate Identifier(s):
OSTI ID: 1394759
Report Number(s):
BNL-114330-2017-JA
Journal ID: ISSN 0027-8424
Grant/Contract Number:  
AC02-98CH10886; SC0012704
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; cluster; electron dynamics; electron localization; temperature dependence

Citation Formats

Zhou, Meng, Jin, Renxi, Sfeir, Matthew Y., Chen, Yuxiang, Song, Yongbo, and Jin, Rongchao. Electron localization in rod-shaped triicosahedral gold nanocluster. United States: N. p., 2017. Web. doi:10.1073/pnas.1704699114.
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Zhou, Meng, Jin, Renxi, Sfeir, Matthew Y., Chen, Yuxiang, Song, Yongbo, & Jin, Rongchao. Electron localization in rod-shaped triicosahedral gold nanocluster. United States. https://doi.org/10.1073/pnas.1704699114
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Zhou, Meng, Jin, Renxi, Sfeir, Matthew Y., Chen, Yuxiang, Song, Yongbo, and Jin, Rongchao. Tue . "Electron localization in rod-shaped triicosahedral gold nanocluster". United States. https://doi.org/10.1073/pnas.1704699114.
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@article{osti_1360862,
title = {Electron localization in rod-shaped triicosahedral gold nanocluster},
author = {Zhou, Meng and Jin, Renxi and Sfeir, Matthew Y. and Chen, Yuxiang and Song, Yongbo and Jin, Rongchao},
abstractNote = {Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons to one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm-1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.},
doi = {10.1073/pnas.1704699114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = ,
volume = ,
place = {United States},
year = {Tue May 30 00:00:00 EDT 2017},
month = {Tue May 30 00:00:00 EDT 2017}
}
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https://doi.org/10.1073/pnas.1704699114
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Works referenced in this record:

Glotaran : A Java -Based Graphical User Interface for the R Package TIMP
journal, January 2012

  • Snellenburg, Joris J.; Laptenok, Sergey P.; Seger, Ralf
  • Journal of Statistical Software, Vol. 49, Issue 3
  • DOI: 10.18637/jss.v049.i03

Conversion of Polydisperse Au Nanoparticles into Monodisperse Au 25 Nanorods and Nanospheres
journal, September 2009

  • Qian, Huifeng; Zhu, Manzhou; Lanni, Eric
  • The Journal of Physical Chemistry C, Vol. 113, Issue 41
  • DOI: 10.1021/jp9073152

Excitons in nanoscale systems
journal, September 2006

  • Scholes, Gregory D.; Rumbles, Garry
  • Nature Materials, Vol. 5, Issue 9
  • DOI: 10.1038/nmat1710

Enhanced Multiple Exciton Dissociation from CdSe Quantum Rods: The Effect of Nanocrystal Shape
journal, June 2012

  • Zhu, Haiming; Lian, Tianquan
  • Journal of the American Chemical Society, Vol. 134, Issue 27
  • DOI: 10.1021/ja304724u

The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors
journal, February 2012

Semiconductor crystallites: a class of large molecules
journal, June 1990

  • Steigerwald, Michael L.; Brus, Louis E.
  • Accounts of Chemical Research, Vol. 23, Issue 6
  • DOI: 10.1021/ar00174a003

Evolution from the plasmon to exciton state in ligand-protected atomically precise gold nanoparticles
journal, October 2016

  • Zhou, Meng; Zeng, Chenjie; Chen, Yuxiang
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13240

Theory for displacive excitation of coherent phonons
journal, January 1992

Oligomeric Gold Clusters with Vertex-Sharing Bi- and Triicosahedral Structures
journal, October 2007

  • Nobusada, Katsuyuki; Iwasa, Takeshi
  • The Journal of Physical Chemistry C, Vol. 111, Issue 39
  • DOI: 10.1021/jp075509w

Observation of trapped-hole diffusion on the surfaces of CdS nanorods
journal, July 2016

  • Utterback, James K.; Grennell, Amanda N.; Wilker, Molly B.
  • Nature Chemistry, Vol. 8, Issue 11
  • DOI: 10.1038/nchem.2566

Exciton delocalization and dynamics in helical π-stacks of self-assembled perylene bisimides
journal, January 2013

  • Lim, Jong Min; Kim, Pyosang; Yoon, Min-Chul
  • Chem. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C2SC21178E

Gold Quantum Boxes: On the Periodicities and the Quantum Confinement in the Au 28 , Au 36 , Au 44 , and Au 52 Magic Series
journal, March 2016

  • Zeng, Chenjie; Chen, Yuxiang; Iida, Kenji
  • Journal of the American Chemical Society, Vol. 138, Issue 12
  • DOI: 10.1021/jacs.5b12747

How a Single Electron Affects the Properties of the “Non-Superatom” Au 25 Nanoclusters
journal, April 2016

Optically Excited Acoustic Vibrations in Quantum-Sized Monolayer-Protected Gold Clusters
journal, May 2010

  • Varnavski, Oleg; Ramakrishna, Guda; Kim, Junhyung
  • ACS Nano, Vol. 4, Issue 6
  • DOI: 10.1021/nn1003524

Ultrafast Relaxation Dynamics of [Au 25 (SR) 18 ] q Nanoclusters: Effects of Charge State
journal, November 2010

  • Qian, Huifeng; Sfeir, Matthew Y.; Jin, Rongchao
  • The Journal of Physical Chemistry C, Vol. 114, Issue 47
  • DOI: 10.1021/jp107915x

Temperature-Dependent Absorption and Ultrafast Luminescence Dynamics of Bi-Icosahedral Au 25 Clusters
journal, October 2013

  • Devadas, Mary Sajini; Thanthirige, Viraj Dhanushka; Bairu, Semere
  • The Journal of Physical Chemistry C, Vol. 117, Issue 44
  • DOI: 10.1021/jp408333h

Screening in crystalline liquids protects energetic carriers in hybrid perovskites
journal, September 2016

Quantitative modeling of the role of surface traps in CdSe/CdS/ZnS nanocrystal photoluminescence decay dynamics
journal, February 2009

  • Jones, M.; Lo, S. S.; Scholes, G. D.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 9
  • DOI: 10.1073/pnas.0809316106

Ultrafast Exciton Dynamics and Light-Driven H 2 Evolution in Colloidal Semiconductor Nanorods and Pt-Tipped Nanorods
journal, February 2015

  • Wu, Kaifeng; Zhu, Haiming; Lian, Tianquan
  • Accounts of Chemical Research, Vol. 48, Issue 3
  • DOI: 10.1021/ar500398g

Superatom State-Resolved Dynamics of the Au 25 (SC 8 H 9 ) 18 – Cluster from Two-Dimensional Electronic Spectroscopy
journal, February 2016

  • Stoll, Tatjana; Sgrò, Enrico; Jarrett, Jeremy W.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b12621

Noble Metals on the Nanoscale: Optical and Photothermal Properties and Some Applications in Imaging, Sensing, Biology, and Medicine
journal, December 2008

  • Jain, Prashant K.; Huang, Xiaohua; El-Sayed, Ivan H.
  • Accounts of Chemical Research, Vol. 41, Issue 12, p. 1578-1586
  • DOI: 10.1021/ar7002804

Theoretical analyses and electron counting rules for high nuclearity clusters
journal, January 1985

  • Mingos, D. Michael P.
  • Journal of the Chemical Society, Chemical Communications, Issue 19
  • DOI: 10.1039/c39850001352

Unique Ultrafast Visible Luminescence in Monolayer-Protected Au 25 Clusters
journal, December 2010

  • Devadas, Mary Sajini; Kim, Junhyung; Sinn, Ekkehard
  • The Journal of Physical Chemistry C, Vol. 114, Issue 51
  • DOI: 10.1021/jp107033n

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities
journal, September 2016

Direct Observation of Excimer-Mediated Intramolecular Electron Transfer in a Cofacially-Stacked Perylene Bisimide Pair
journal, July 2016

  • Sung, Jooyoung; Nowak-Król, Agnieszka; Schlosser, Felix
  • Journal of the American Chemical Society, Vol. 138, Issue 29
  • DOI: 10.1021/jacs.6b04591

Emergence of hierarchical structural complexities in nanoparticles and their assembly
journal, December 2016

Efficient Extraction of Trapped Holes from Colloidal CdS Nanorods
journal, August 2015

  • Wu, Kaifeng; Du, Yongling; Tang, Hua
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b04564

Atomic clusters: Building blocks for a class of solids
journal, May 1995

Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides
journal, October 2015

  • Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9646

Thiolated Gold Nanowires: Metallic versus Semiconducting
journal, July 2009

  • Jiang, De-en; Nobusada, Katsuyuki; Luo, Weidong
  • ACS Nano, Vol. 3, Issue 8
  • DOI: 10.1021/nn900498c

Single-molecule spectroscopy and femtosecond transient absorption studies on the excitation energy transfer process in ApcE(1–240) dimers
journal, January 2015

  • Long, Saran; Zhou, Meng; Tang, Kun
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 20
  • DOI: 10.1039/C5CP01687H

Total Structure and Optical Properties of a Phosphine/Thiolate-Protected Au 24 Nanocluster
journal, December 2012

  • Das, Anindita; Li, Tao; Nobusada, Katsuyuki
  • Journal of the American Chemical Society, Vol. 134, Issue 50
  • DOI: 10.1021/ja3101566

Quantum confined colloidal nanorod heterostructures for solar-to-fuel conversion
journal, January 2016

  • Wu, Kaifeng; Lian, Tianquan
  • Chemical Society Reviews, Vol. 45, Issue 14
  • DOI: 10.1039/C5CS00472A

An Ultrafast Look at Au Nanoclusters
journal, May 2013

  • Yau, Sung Hei; Varnavski, Oleg; Goodson, Theodore
  • Accounts of Chemical Research, Vol. 46, Issue 7
  • DOI: 10.1021/ar300280w

Molecule-like Photodynamics of Au 102 ( p MBA) 44 Nanocluster
journal, February 2015

  • Mustalahti, Satu; Myllyperkiö, Pasi; Malola, Sami
  • ACS Nano, Vol. 9, Issue 3
  • DOI: 10.1021/nn506711a

The Magic Au 60 Nanocluster: A New Cluster-Assembled Material with Five Au 13 Building Blocks
journal, May 2015

  • Song, Yongbo; Fu, Fangyu; Zhang, Jun
  • Angewandte Chemie International Edition, Vol. 54, Issue 29
  • DOI: 10.1002/anie.201501830

Clusters of clusters: self-organization and self-similarity in the intermediate stages of cluster growth of Au-Ag supraclusters.
journal, June 1991

  • Teo, B. K.; Zhang, H.
  • Proceedings of the National Academy of Sciences, Vol. 88, Issue 12
  • DOI: 10.1073/pnas.88.12.5067

Slow-Reduction Synthesis of a Thiolate-Protected One-Dimensional Gold Cluster Showing an Intense Near-Infrared Absorption
journal, June 2015

  • Takano, Shinjiro; Yamazoe, Seiji; Koyasu, Kiichirou
  • Journal of the American Chemical Society, Vol. 137, Issue 22
  • DOI: 10.1021/jacs.5b03251

Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster and Optical Properties
journal, May 2008

  • Zhu, Manzhou; Aikens, Christine M.; Hollander, Frederick J.
  • Journal of the American Chemical Society, Vol. 130, Issue 18, p. 5883-5885
  • DOI: 10.1021/ja801173r

Ultrafast Relaxation Dynamics of Rod-Shaped 25-Atom Gold Nanoclusters
journal, March 2011

  • Sfeir, Matthew Y.; Qian, Huifeng; Nobusada, Katsuyuki
  • The Journal of Physical Chemistry C, Vol. 115, Issue 14
  • DOI: 10.1021/jp110703e

Coherent Intrachain Energy Migration in a Conjugated Polymer at Room Temperature
journal, January 2009

Temperature-Dependent Optical Absorption Properties of Monolayer-Protected Au 25 and Au 38 Clusters
journal, October 2011

  • Devadas, Mary Sajini; Bairu, Semere; Qian, Huifeng
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz2012897

Optical Studies of Dynamics in Noble Metal Nanostructures
journal, June 2011

Charge Redistribution Effects on the UV–Vis Spectra of Small Ligated Gold Clusters: a Computational Study
journal, January 2015

  • Lugo, G.; Schwanen, V.; Fresch, B.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 20
  • DOI: 10.1021/jp511120j

Band Gap Variation of Size- and Shape-Controlled Colloidal CdSe Quantum Rods
journal, July 2001

  • Li, Liang-shi; Hu, Jiangtao; Yang, Weidong
  • Nano Letters, Vol. 1, Issue 7
  • DOI: 10.1021/nl015559r

van der Waals Solids from Self-Assembled Nanoscale Building Blocks
journal, January 2016

Formation of Al13I-: Evidence for the Superhalogen Character of Al13
journal, April 2004

Global and target analysis of time-resolved spectra
journal, July 2004

  • van Stokkum, Ivo H. M.; Larsen, Delmar S.; van Grondelle, Rienk
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1657, Issue 2-3
  • DOI: 10.1016/j.bbabio.2004.04.011

Biicosahedral Gold Clusters [Au 25 (PPh 3 ) 10 (SC n H 2 n +1 ) 5 Cl 2 ] 2+ ( n = 2−18):  A Stepping Stone to Cluster-Assembled Materials
journal, June 2007

  • Shichibu, Yukatsu; Negishi, Yuichi; Watanabe, Takahito
  • The Journal of Physical Chemistry C, Vol. 111, Issue 22
  • DOI: 10.1021/jp073101t

Exciton Localization and Dissociation Dynamics in CdS and CdS–Pt Quantum Confined Nanorods: Effect of Nonuniform Rod Diameters
journal, July 2014

  • Wu, Kaifeng; Rodríguez-Córdoba, William; Lian, Tianquan
  • The Journal of Physical Chemistry B, Vol. 118, Issue 49
  • DOI: 10.1021/jp504703t
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