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Title: Ultrafast Relaxation Dynamics of Au 38 (SC 2 H 4 Ph) 24 Nanoclusters and Effects of Structural Isomerism

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [2]; ORCiD logo [1]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States). Dept. of Chemistry
  2. 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
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
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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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1394758
Report Number(s):
BNL-114329-2017-JA; KC0403020
Journal Information:
Journal of Physical Chemistry. C, Vol. 121, Issue 20; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

References (49)

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities journal September 2016
Quantum Sized Gold Nanoclusters with Atomic Precision journal June 2012
Understanding Ligand-Exchange Reactions on Thiolate-Protected Gold Clusters by Probing Isomer Distributions Using Reversed-Phase High-Performance Liquid Chromatography journal July 2015
Balancing the Rate of Cluster Growth and Etching for Gram-Scale Synthesis of Thiolate-Protected Au 25 Nanoclusters with Atomic Precision journal March 2014
Structural patterns at all scales in a nonmetallic chiral Au 133 (SR) 52 nanoparticle journal March 2015
Total Structure Determination of Au 21 (S-Adm) 15 and Geometrical/Electronic Structure Evolution of Thiolated Gold Nanoclusters journal August 2016
Controlling the Atomic Structure of Au 30 Nanoclusters by a Ligand-Based Strategy journal April 2016
Structural isomerism in gold nanoparticles revealed by X-ray crystallography journal October 2015
An Ultrafast Look at Au Nanoclusters journal May 2013
Ultrafast Relaxation Dynamics of [Au 25 (SR) 18 ] q Nanoclusters: Effects of Charge State journal November 2010
Ultrafast Relaxation Dynamics of Rod-Shaped 25-Atom Gold Nanoclusters journal March 2011
Long-Lived Charge-Separated States in Ligand-Stabilized Silver Clusters journal July 2012
Intramolecular Charge Transfer and Solvation Dynamics of Thiolate-Protected Au 20 (SR) 16 Clusters Studied by Ultrafast Measurement journal September 2013
Evolution from the plasmon to exciton state in ligand-protected atomically precise gold nanoparticles journal October 2016
Dynamic Diglyme-Mediated Self-Assembly of Gold Nanoclusters journal October 2015
Relaxation dynamics of Au25L18 nanoclusters studied by femtosecond time-resolved near infrared transient absorption spectroscopy journal January 2012
Superatom State-Resolved Dynamics of the Au 25 (SC 8 H 9 ) 18 – Cluster from Two-Dimensional Electronic Spectroscopy journal February 2016
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
Photodynamics of a Molecular Water-Soluble Nanocluster Identified as Au 130 ( p MBA) 50 journal August 2015
Directional Electron Transfer in Chromophore-Labeled Quantum-Sized Au 25 Clusters: Au 25 as an Electron Donor journal April 2010
Optical Studies of Dynamics in Noble Metal Nanostructures journal June 2011
Ultrafast Resonant Dynamics of Surface Plasmons in Gold Nanorods journal January 2007
Femtosecond transient-absorption dynamics of colloidal gold nanorods: Shape independence of the electron-phonon relaxation time journal March 2000
Ultrafast Acoustic Vibrations of Bimetallic Nanoparticles journal January 2015
Coherent Vibrational Oscillations of Hollow Gold Nanospheres journal January 2011
Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster and Optical Properties
  • Zhu, Manzhou; Aikens, Christine M.; Hollander, Frederick J.
  • Journal of the American Chemical Society, Vol. 130, Issue 18, p. 5883-5885 https://doi.org/10.1021/ja801173r
journal May 2008
Effects of single atom doping on the ultrafast electron dynamics of M 1 Au 24 (SR) 18 (M = Pd, Pt) nanoclusters journal January 2016
Temperature-Dependent Absorption and Ultrafast Exciton Relaxation Dynamics in MAu 24 (SR) 18 Clusters (M = Pt, Hg): Role of the Central Metal Atom journal September 2016
Total Structure Determination of Thiolate-Protected Au 38 Nanoparticles journal June 2010
Chirality in Thiolate-Protected Gold Clusters journal February 2014
Chiral 38-Gold-Atom Nanoclusters: Synthesis and Chiroptical Properties journal October 2013
Hierarchy of bond stiffnesses within icosahedral-based gold clusters protected by thiolates journal January 2016
Palladium doping of magic gold cluster Au 38 (SC 2 H 4 Ph) 24 : formation of Pd 2 Au 36 (SC 2 H 4 Ph) 24 with higher stability than Au 38 (SC 2 H 4 Ph) 24 journal January 2012
Temperature-Dependent Photoluminescence of Structurally-Precise Quantum-Confined Au 25 (SC 8 H 9 ) 18 and Au 38 (SC 12 H 25 ) 24 Metal Nanoparticles journal September 2014
CeO2-supported Au38(SR)24 nanocluster catalysts for CO oxidation: a comparison of ligand-on and -off catalysts journal January 2013
Temperature-Dependent Absorption and Ultrafast Luminescence Dynamics of Bi-Icosahedral Au 25 Clusters journal October 2013
Temperature-Dependent Optical Absorption Properties of Monolayer-Protected Au 25 and Au 38 Clusters journal October 2011
Structural Prediction of Thiolate-Protected Au 38 : A Face-Fused Bi-icosahedral Au Core journal June 2008
Chirality and Electronic Structure of the Thiolate-Protected Au 38 Nanocluster journal June 2010
Theoretical Insights into the Origin of Photoluminescence of Au 25 (SR) 18 – Nanoparticles journal August 2016
Generation of Singlet Oxygen by Photoexcited Au 25 (SR) 18 Clusters journal April 2014
Electron−Phonon Coupling in CdSe Nanocrystals journal April 2010
Time-Resolved Studies of the Acoustic Vibrational Modes of Metal and Semiconductor Nano-objects journal February 2014
Vibrational Coupling Modulation in n- Alkanethiolate Protected Au 25 (SR) 18 0 Clusters journal October 2016
Size dependent, state-resolved studies of exciton-phonon couplings in strongly confined semiconductor quantum dots journal June 2008
Isomerism in Au 28 (SR) 20 Nanocluster and Stable Structures journal January 2016
Size-Focusing Synthesis, Optical and Electrochemical Properties of Monodisperse Au 38 (SC 2 H 4 Ph) 24 Nanoclusters journal October 2009
Glotaran : A Java -Based Graphical User Interface for the R Package TIMP journal January 2012
Global and target analysis of time-resolved spectra journal July 2004

Cited By (5)

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Understanding energy transfer with luminescent gold nanoclusters: a promising new transduction modality for biorelated applications journal January 2017
An overview on the current understanding of the photophysical properties of metal nanoclusters and their potential applications journal January 2019
Gold Nanoclusters: Bridging Gold Complexes and Plasmonic Nanoparticles in Photophysical Properties journal June 2019
Opportunities and challenges in energy and electron transfer of nanocluster based hybrid materials and their sensing applications journal January 2019

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Related Subjects

36 MATERIALS SCIENCE
Center for Functional Nanomaterials