skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters

Abstract

The transition from molecular to plasmonic behaviour in metal nanoparticles with increasing size remains a central question in nanoscience. Here, we report that the giant 246-gold-atom nanocluster (2.2 nm in gold core diameter) protected by 80 thiolate ligands is surprisingly non-metallic based on UV/Vis and femtosecond transient absorption spectroscopy as well as electrochemical measurements. Specifically, the Au246 nanocluster exhibits multiple excitonic peaks in transient absorption spectra and electron dynamics independent of the pump power, which are in contrast to the behaviour of metallic gold nanoparticles. Moreover, a prominent oscillatory feature with frequency of 0.5 THz can be observed in almost all the probe wavelengths. The phase and amplitude analysis of the oscillation suggests that it arises from the wavepacket motion on the ground state potential energy surface, which also indicates the presence of a small band-gap and thus non-metallic or molecular-like behaviour.

Authors:
 [1];  [1];  [1];  [2];  [2]; ORCiD logo [3];  [1];  [1]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Chemistry
  2. Georgia State Univ., Atlanta (Georgia). Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Lab. (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)
OSTI Identifier:
1426449
Alternate Identifier(s):
OSTI ID: 1410131
Report Number(s):
BNL-203329-2018-JAAM
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
SC0012704; FA9550-15-1-9999; FA9550-15-1-0154; AC02-98CH10886
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 51; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electron dynamics; gold; nanoparticles; photophysics; ultrafast spectroscopy

Citation Formats

Zhou, Meng, Zeng, Chenjie, Song, Yongbo, Padelford, Jonathan W., Wang, Gangli, Sfeir, Matthew Y., Higaki, Tatsuya, and Jin, Rongchao. On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters. United States: N. p., 2017. Web. doi:10.1002/anie.201709095.
Zhou, Meng, Zeng, Chenjie, Song, Yongbo, Padelford, Jonathan W., Wang, Gangli, Sfeir, Matthew Y., Higaki, Tatsuya, & Jin, Rongchao. On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters. United States. doi:10.1002/anie.201709095.
Zhou, Meng, Zeng, Chenjie, Song, Yongbo, Padelford, Jonathan W., Wang, Gangli, Sfeir, Matthew Y., Higaki, Tatsuya, and Jin, Rongchao. Wed . "On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters". United States. doi:10.1002/anie.201709095. https://www.osti.gov/servlets/purl/1426449.
@article{osti_1426449,
title = {On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters},
author = {Zhou, Meng and Zeng, Chenjie and Song, Yongbo and Padelford, Jonathan W. and Wang, Gangli and Sfeir, Matthew Y. and Higaki, Tatsuya and Jin, Rongchao},
abstractNote = {The transition from molecular to plasmonic behaviour in metal nanoparticles with increasing size remains a central question in nanoscience. Here, we report that the giant 246-gold-atom nanocluster (2.2 nm in gold core diameter) protected by 80 thiolate ligands is surprisingly non-metallic based on UV/Vis and femtosecond transient absorption spectroscopy as well as electrochemical measurements. Specifically, the Au246 nanocluster exhibits multiple excitonic peaks in transient absorption spectra and electron dynamics independent of the pump power, which are in contrast to the behaviour of metallic gold nanoparticles. Moreover, a prominent oscillatory feature with frequency of 0.5 THz can be observed in almost all the probe wavelengths. The phase and amplitude analysis of the oscillation suggests that it arises from the wavepacket motion on the ground state potential energy surface, which also indicates the presence of a small band-gap and thus non-metallic or molecular-like behaviour.},
doi = {10.1002/anie.201709095},
journal = {Angewandte Chemie (International Edition)},
number = 51,
volume = 56,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

Transition from nanoparticle to molecular behavior: a femtosecond transient absorption study of a size-selected 28 atom gold cluster
journal, April 2002


Theory for displacive excitation of coherent phonons
journal, January 1992


Damping of acoustic vibrations in gold nanoparticles
journal, July 2009

  • Pelton, Matthew; Sader, John E.; Burgin, Julien
  • Nature Nanotechnology, Vol. 4, Issue 8
  • DOI: 10.1038/nnano.2009.192

Structural patterns at all scales in a nonmetallic chiral Au 133 (SR) 52 nanoparticle
journal, March 2015

  • Zeng, Chenjie; Chen, Yuxiang; Kirschbaum, Kristin
  • Science Advances, Vol. 1, Issue 2
  • DOI: 10.1126/sciadv.1500045

Structural and bonding patterns in gold clusters
journal, January 2015


Broad-Band Impulsive Vibrational Spectroscopy of Excited Electronic States in the Time Domain
journal, March 2013

  • Liebel, Matz; Kukura, Philipp
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 8
  • DOI: 10.1021/jz4004203

Damping of Acoustic Vibrations of Single Gold Nanoparticles Optically Trapped in Water
journal, January 2012

  • Ruijgrok, Paul V.; Zijlstra, Peter; Tchebotareva, Anna L.
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl204311q

Broadband Transient Absorption and Two-Dimensional Electronic Spectroscopy of Methylene Blue
journal, August 2015

  • Dean, Jacob C.; Rafiq, Shahnawaz; Oblinsky, Daniel G.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 34
  • DOI: 10.1021/acs.jpca.5b06126

Ultrafast Electronic Relaxation and Vibrational Cooling Dynamics of Au 144 (SC 2 H 4 Ph) 60 Nanocluster Probed by Transient Mid-IR Spectroscopy
journal, July 2014

  • Mustalahti, Satu; Myllyperkiö, Pasi; Lahtinen, Tanja
  • The Journal of Physical Chemistry C, Vol. 118, Issue 31
  • DOI: 10.1021/jp505464z

Coherent Excitation of Vibrational Modes in Metallic Nanoparticles
journal, May 2006


Diameter Dependence of the Excitation Spectra of Silver and Gold Nanorods
journal, May 2013

  • Guidez, Emilie B.; Aikens, Christine M.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 23
  • DOI: 10.1021/jp4023103

Ultrafast Electron Dynamics and Optical Nonlinearities in Metal Nanoparticles
journal, March 2001

  • Voisin, Christophe; Del Fatti, Natalia; Christofilos, Dimitris
  • The Journal of Physical Chemistry B, Vol. 105, Issue 12
  • DOI: 10.1021/jp0038153

Gold Nanoparticle Capping Layers: Structure, Dynamics, and Surface Enhancement Measured Using 2D-IR Spectroscopy
journal, November 2012


Atomically precise gold nanocrystal molecules with surface plasmon resonance
journal, January 2012

  • Qian, H.; Zhu, Y.; Jin, R.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 3
  • DOI: 10.1073/pnas.1115307109

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

Femtosecond Wavepacket Spectroscopy: Influence of Temperature, Wavelength, and Pulse Duration
journal, March 1995

  • Jonas, David M.; Bradforth, Stephen E.; Passino, Sean A.
  • The Journal of Physical Chemistry, Vol. 99, Issue 9, p. 2594-2608
  • DOI: 10.1021/j100009a018

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

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

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


Excitation-Dependence of Plasmon-Induced Hot Electrons in Gold Nanoparticles
journal, September 2017

  • Minutella, Emanuele; Schulz, Florian; Lange, Holger
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 19
  • DOI: 10.1021/acs.jpclett.7b02043

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


Gold Nanoparticle Capping Layers: Structure, Dynamics, and Surface Enhancement Measured Using 2D-IR Spectroscopy
journal, November 2012

  • Donaldson, Paul M.; Hamm, Peter
  • Angewandte Chemie International Edition, Vol. 52, Issue 2
  • DOI: 10.1002/anie.201204973

Selective Excitation of Vibrational Wave Packet Motion Using Chirped Pulses
journal, November 1995


O PTICAL P ROPERTIES AND U LTRAFAST D YNAMICS OF M ETALLIC N ANOCRYSTALS
journal, October 2003


Ultrafast transient absorption revisited: Phase-flips, spectral fingers, and other dynamical features
journal, May 2016

  • Cina, Jeffrey A.; Kovac, Philip A.; Jumper, Chanelle C.
  • The Journal of Chemical Physics, Vol. 144, Issue 17
  • DOI: 10.1063/1.4947568

Unraveling a generic growth pattern in structure evolution of thiolate-protected gold nanoclusters
journal, January 2016


Critical Size for the Observation of Quantum Confinement in Optically Excited Gold Clusters
journal, January 2010

  • Varnavski, Oleg; Ramakrishna, Guda; Kim, Junhyung
  • Journal of the American Chemical Society, Vol. 132, Issue 1
  • DOI: 10.1021/ja907984r

Subpicosecond time-resolved coherent-phonon oscillations in GaAs
journal, August 1990


Gold Nanoparticles for Biology and Medicine
journal, April 2010

  • Giljohann, David A.; Seferos, Dwight S.; Daniel, Weston L.
  • Angewandte Chemie International Edition, Vol. 49, Issue 19, p. 3280-3294
  • DOI: 10.1002/anie.200904359

Nonequilibrium Electron Interactions in Metal Films
journal, July 1998


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

Information on quantum states pervades the visible spectrum of the ubiquitous Au144(SR)60 gold nanocluster
journal, April 2014

  • Weissker, H. -Ch.; Escobar, H. Barron; Thanthirige, V. D.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4785

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

Intramolecular Charge Transfer and Solvation Dynamics of Thiolate-Protected Au 20 (SR) 16 Clusters Studied by Ultrafast Measurement
journal, September 2013

  • Zhou, Meng; Vdović, Silvije; Long, Saran
  • The Journal of Physical Chemistry A, Vol. 117, Issue 40
  • DOI: 10.1021/jp406336q

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

Size dependent, state-resolved studies of exciton-phonon couplings in strongly confined semiconductor quantum dots
journal, June 2008


Quantum mechanical origin of the plasmon: from molecular systems to nanoparticles
journal, January 2014

  • Guidez, Emilie B.; Aikens, Christine M.
  • Nanoscale, Vol. 6, Issue 20
  • DOI: 10.1039/C4NR02225D

Femtosecond Chirped Pulse Excitation of Vibrational Wave Packets in LD690 and Bacteriorhodopsin
journal, April 1998

  • Bardeen, C. J.; Wang, Q.; Shank, C. V.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 17
  • DOI: 10.1021/jp980346k

Thousand-fold Enhancement of Single-Molecule Fluorescence Near a Single Gold Nanorod
journal, December 2012

  • Yuan, Haifeng; Khatua, Saumyakanti; Zijlstra, Peter
  • Angewandte Chemie International Edition, Vol. 52, Issue 4
  • DOI: 10.1002/anie.201208125

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

Ultrafast Photochemistry in Liquids
journal, April 2013


Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au 130 ( p MBA) 50
journal, August 2015

  • Mustalahti, Satu; Myllyperkiö, Pasi; Lahtinen, Tanja
  • The Journal of Physical Chemistry C, Vol. 119, Issue 34
  • DOI: 10.1021/acs.jpcc.5b07672

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


Visualization of coherent nuclear motion in a membrane protein by femtosecond spectroscopy
journal, May 1993

  • Vos, Marten H.; Rappaport, Fabrice; Lambry, Jean-Christophe
  • Nature, Vol. 363, Issue 6427
  • DOI: 10.1038/363320a0

Size Dependence of the Optical Response of Spherical Sodium Clusters
journal, February 1995


Slow Intramolecular Vibrational Relaxation Leads to Long-Lived Excited-State Wavepackets
journal, August 2016

  • Rafiq, Shahnawaz; Scholes, Gregory D.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 34
  • DOI: 10.1021/acs.jpca.6b07796

Goldnanopartikel in Biologie und Medizin
journal, April 2010

  • Giljohann, David A.; Seferos, Dwight S.; Daniel, Weston L.
  • Angewandte Chemie, Vol. 122, Issue 19
  • DOI: 10.1002/ange.200904359

Thousand-fold Enhancement of Single-Molecule Fluorescence Near a Single Gold Nanorod
journal, December 2012

  • Yuan, Haifeng; Khatua, Saumyakanti; Zijlstra, Peter
  • Angewandte Chemie, Vol. 125, Issue 4
  • DOI: 10.1002/ange.201208125

Plasmonic twinned silver nanoparticles with molecular precision
journal, September 2016

  • Yang, Huayan; Wang, Yu; Chen, Xi
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12809

Optical Properties and Electronic Energy Relaxation of Metallic Au 144 (SR) 60 Nanoclusters
journal, November 2013

  • Yi, Chongyue; Tofanelli, Marcus A.; Ackerson, Christopher J.
  • Journal of the American Chemical Society, Vol. 135, Issue 48
  • DOI: 10.1021/ja409998j

Photoabsorption spectra of sodium clusters
journal, February 1991


A Critical Size for Emergence of Nonbulk Electronic and Geometric Structures in Dodecanethiolate-Protected Au Clusters
journal, January 2015

  • Negishi, Yuichi; Nakazaki, Tafu; Malola, Sami
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja5109968

Evolution of Nonlinear Optical Properties: From Gold Atomic Clusters to Plasmonic Nanocrystals
journal, January 2012

  • Philip, Reji; Chantharasupawong, Panit; Qian, Huifeng
  • Nano Letters, Vol. 12, Issue 9
  • DOI: 10.1021/nl301988v

    Works referencing / citing this record:

    Linker Flexibility-Dependent Cluster Transformations and Cluster-Controlled Luminescence in Isostructural Silver Cluster-Assembled Materials (SCAMs)
    journal, February 2019

    • Wang, Jia-Yin; Huang, Ren-Wu; Wei, Zhong
    • Chemistry - A European Journal, Vol. 25, Issue 13
    • DOI: 10.1002/chem.201805808

    Anomalous phonon relaxation in Au 333 (SR) 79 nanoparticles with nascent plasmons
    journal, June 2019

    • Higaki, Tatsuya; Zhou, Meng; He, Guiying
    • Proceedings of the National Academy of Sciences, Vol. 116, Issue 27
    • DOI: 10.1073/pnas.1904337116

    Au 130− x Ag x Nanoclusters with Non-Metallicity: A Drum of Silver-Rich Sites Enclosed in a Marks-Decahedral Cage of Gold-Rich Sites
    journal, November 2019

    • Higaki, Tatsuya; Liu, Chong; Morris, David J.
    • Angewandte Chemie International Edition, Vol. 58, Issue 52
    • DOI: 10.1002/anie.201908694

    Au 130− x Ag x Nanoclusters with Non-Metallicity: A Drum of Silver-Rich Sites Enclosed in a Marks-Decahedral Cage of Gold-Rich Sites
    journal, November 2019

    • Higaki, Tatsuya; Liu, Chong; Morris, David J.
    • Angewandte Chemie International Edition, Vol. 58, Issue 52
    • DOI: 10.1002/anie.201908694

    Linker Flexibility-Dependent Cluster Transformations and Cluster-Controlled Luminescence in Isostructural Silver Cluster-Assembled Materials (SCAMs)
    journal, February 2019

    • Wang, Jia-Yin; Huang, Ren-Wu; Wei, Zhong
    • Chemistry - A European Journal, Vol. 25, Issue 13
    • DOI: 10.1002/chem.201805808

    Anomalous phonon relaxation in Au 333 (SR) 79 nanoparticles with nascent plasmons
    journal, June 2019

    • Higaki, Tatsuya; Zhou, Meng; He, Guiying
    • Proceedings of the National Academy of Sciences, Vol. 116, Issue 27
    • DOI: 10.1073/pnas.1904337116