Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters
Abstract
Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atommore »
- Authors:
-
- Carnegie Mellon Univ., Pittsburgh, PA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Institute for Molecular Science, Myodaiji (Japan); Kyoto Univ., Kyoto (Japan)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1326756
- Report Number(s):
- BNL-112653-2016-JA
Journal ID: ISSN 2040-3364; NANOHL; R&D Project: 16063; 16058; KC0403020
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 13; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; doped nanoclusters; electronic properties; excited state dynamics; transient absorption; Center for Functional Nanomaterials
Citation Formats
Zhou, Meng, Qian, Huifeng, Sfeir, Matthew Y., Nobusada, Katsuyuki, and Jin, Rongchao. Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters. United States: N. p., 2016.
Web. doi:10.1039/c6nr01008c.
Zhou, Meng, Qian, Huifeng, Sfeir, Matthew Y., Nobusada, Katsuyuki, & Jin, Rongchao. Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters. United States. https://doi.org/10.1039/c6nr01008c
Zhou, Meng, Qian, Huifeng, Sfeir, Matthew Y., Nobusada, Katsuyuki, and Jin, Rongchao. Mon .
"Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters". United States. https://doi.org/10.1039/c6nr01008c. https://www.osti.gov/servlets/purl/1326756.
@article{osti_1326756,
title = {Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters},
author = {Zhou, Meng and Qian, Huifeng and Sfeir, Matthew Y. and Nobusada, Katsuyuki and Jin, Rongchao},
abstractNote = {Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. As a result, the detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.},
doi = {10.1039/c6nr01008c},
journal = {Nanoscale},
number = 13,
volume = 8,
place = {United States},
year = {Mon Feb 29 00:00:00 EST 2016},
month = {Mon Feb 29 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
Optical Studies of Dynamics in Noble Metal Nanostructures
journal, June 2011
- Hartland, Gregory V.
- Chemical Reviews, Vol. 111, Issue 6
An Ultrafast Look at Au Nanoclusters
journal, May 2013
- Yau, Sung Hei; Varnavski, Oleg; Goodson, Theodore
- Accounts of Chemical Research, Vol. 46, Issue 7
Ultrafast Photoinduced Charge Separation in Metal–Semiconductor Nanohybrids
journal, July 2012
- Mongin, Denis; Shaviv, Ehud; Maioli, Paolo
- ACS Nano, Vol. 6, Issue 8
Tuning Ag 29 nanocluster light emission from red to blue with one and two-photon excitation
journal, January 2016
- Russier-Antoine, Isabelle; Bertorelle, Franck; Hamouda, Ramzi
- Nanoscale, Vol. 8, Issue 5
Coherent Vibrational Oscillations of Hollow Gold Nanospheres
journal, January 2011
- Newhouse, Rebecca J.; Wang, Haining; Hensel, Jennifer K.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 3
Atomically Precise Gold Nanoclusters as New Model Catalysts
journal, March 2013
- Li, Gao; Jin, Rongchao
- Accounts of Chemical Research, Vol. 46, Issue 8
Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study
journal, January 2015
- Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.
- Nanoscale, Vol. 7, Issue 11
Polarization properties of fluorescent BSA protected Au25 nanoclusters
journal, January 2013
- Raut, Sangram; Chib, Rahul; Rich, Ryan
- Nanoscale, Vol. 5, Issue 8
Resonance energy transfer between fluorescent BSA protected Au nanoclusters and organic fluorophores
journal, January 2014
- Raut, Sangram; Rich, Ryan; Fudala, Rafal
- Nanoscale, Vol. 6, Issue 1
Non-linear optical properties of gold quantum clusters. The smaller the better
journal, January 2014
- Russier-Antoine, Isabelle; Bertorelle, Franck; Vojkovic, Marin
- Nanoscale, Vol. 6, Issue 22
Biocompatible glutathione capped gold clusters as one- and two-photon excitation fluorescence contrast agents for live cells imaging
journal, January 2011
- Polavarapu, Lakshminarayana; Manna, Manoj; Xu, Qing-Hua
- Nanoscale, Vol. 3, Issue 2
Au 25 cluster functionalized metal–organic nanostructures for magnetically targeted photodynamic/photothermal therapy triggered by single wavelength 808 nm near-infrared light
journal, January 2015
- Yang, Dan; Yang, Guixin; Gai, Shili
- Nanoscale, Vol. 7, Issue 46
Doping and alloying in atomically precise gold nanoparticles
journal, January 2014
- Jin, Rongchao; Nobusada, Katsuyuki
- Nano Research, Vol. 7, Issue 3
Isolation, structure, and stability of a dodecanethiolate-protected Pd1Au24 cluster
journal, January 2010
- Negishi, Yuichi; Kurashige, Wataru; Niihori, Yoshiki
- Physical Chemistry Chemical Physics, Vol. 12, Issue 23
Metal Exchange Method Using Au 25 Nanoclusters as Templates for Alloy Nanoclusters with Atomic Precision
journal, March 2015
- Wang, Shuxin; Song, Yongbo; Jin, Shan
- Journal of the American Chemical Society, Vol. 137, Issue 12
Mono-Mercury Doping of Au 25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry
journal, July 2015
- Liao, Lingwen; Zhou, Shiming; Dai, Yafei
- Journal of the American Chemical Society, Vol. 137, Issue 30
Continuous modulation of electronic structure of stable thiolate-protected Au25 cluster by Ag doping
journal, January 2010
- Negishi, Yuichi; Iwai, Takeyuki; Ide, Mao
- Chemical Communications, Vol. 46, Issue 26
Crystal Structure of the PdAu 24 (SR) 18 0 Superatom
journal, January 2016
- Tofanelli, Marcus A.; Ni, Thomas W.; Phillips, Billy D.
- Inorganic Chemistry, Vol. 55, Issue 3
Monoplatinum Doping of Gold Nanoclusters and Catalytic Application
journal, September 2012
- Qian, Huifeng; Jiang, De-en; Li, Gao
- Journal of the American Chemical Society, Vol. 134, Issue 39
From Superatomic Au 25 (SR) 18 − to Superatomic M@Au 24 (SR) 18 q Core−Shell Clusters
journal, April 2009
- Jiang, De-en; Dai, Sheng
- Inorganic Chemistry, Vol. 48, Issue 7
Dopant Location, Local Structure, and Electronic Properties of Au 24 Pt(SR) 18 Nanoclusters
journal, December 2012
- Christensen, Stephen L.; MacDonald, Mark A.; Chatt, Amares
- The Journal of Physical Chemistry C, Vol. 116, Issue 51
Ligand-Protected Gold Alloy Clusters: Doping the Superatom
journal, August 2009
- Walter, Michael; Moseler, Michael
- The Journal of Physical Chemistry C, Vol. 113, Issue 36
Formation of a Pd@Au 12 Superatomic Core in Au 24 Pd 1 (SC 12 H 25 ) 18 Probed by 197 Au Mössbauer and Pd K-Edge EXAFS Spectroscopy
journal, October 2013
- Negishi, Yuichi; Kurashige, Wataru; Kobayashi, Yasuhiro
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
Enhancement in Aerobic Alcohol Oxidation Catalysis of Au 25 Clusters by Single Pd Atom Doping
journal, June 2012
- Xie, Songhai; Tsunoyama, Hironori; Kurashige, Wataru
- ACS Catalysis, Vol. 2, Issue 7
Direct probe of size-dependent electronic relaxation in single-sized Au and nearly monodisperse Pt colloidal nano-particles
journal, May 1997
- Smith, Brian A.; Zhang, Jin Z.; Giebel, Ursula
- Chemical Physics Letters, Vol. 270, Issue 1-2
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
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
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
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
Ultrafast relaxation dynamics of phosphine-protected, rod-shaped Au 20 clusters: interplay between solvation and surface trapping
journal, January 2014
- Zhou, Meng; Long, Saran; Wan, Xiankai
- Phys. Chem. Chem. Phys., Vol. 16, Issue 34
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
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
Ultrafast static and diffusion-controlled electron transfer at Ag 29 nanocluster/molecular acceptor interfaces
journal, January 2016
- Aly, Shawkat M.; AbdulHalim, Lina G.; Besong, Tabot M. D.
- Nanoscale, Vol. 8, Issue 10
Femtosecond Relaxation Dynamics of Au 25 L 18 − Monolayer-Protected Clusters
journal, May 2009
- Miller, Stephen A.; Womick, Jordan M.; Parker, Joseph F.
- The Journal of Physical Chemistry C, Vol. 113, Issue 22
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
Relaxation dynamics of Au25L18 nanoclusters studied by femtosecond time-resolved near infrared transient absorption spectroscopy
journal, January 2012
- Green, Thomas D.; Knappenberger, Kenneth L.
- Nanoscale, Vol. 4, Issue 14
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
Ultrafast Relaxation Dynamics of Luminescent Rod-Shaped, Silver-Doped Ag x Au 25– x Clusters
journal, July 2015
- Zhou, Meng; Zhong, Juan; Wang, Shuxin
- The Journal of Physical Chemistry C, Vol. 119, Issue 32
Size-Dependent Excited State Behavior of Glutathione-Capped Gold Clusters and Their Light-Harvesting Capacity
journal, July 2014
- Stamplecoskie, Kevin G.; Kamat, Prashant V.
- Journal of the American Chemical Society, Vol. 136, Issue 31
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
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
Ultrafast exciton dynamics after Soret- or Q-band excitation of a directly β,β′-linked bisporphyrin
journal, January 2012
- Kullmann, Martin; Hipke, Arthur; Nuernberger, Patrick
- Physical Chemistry Chemical Physics, Vol. 14, Issue 22
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
Energy-adjustedab initio pseudopotentials for the second and third row transition elements
journal, January 1990
- Andrae, D.; H�u�ermann, U.; Dolg, M.
- Theoretica Chimica Acta, Vol. 77, Issue 2
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
Nonlinear Optical Signatures of Core and Ligand Electronic States in Au 24 PdL 18
journal, April 2010
- Miller, Stephen A.; Fields-Zinna, Christina A.; Murray, Royce W.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 9
Different Methods of Increasing the Mechanical Strength of Gold Nanocages
journal, November 2012
- Mahmoud, Mahmoud A.; Szymanski, Paul; El-Sayed, Mostafa A.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 23
Works referencing / citing this record:
Nature of mercury inclusion in intermediate 6‐valence electron [M@Au 8 Hg x (PPh 3 ) 8 ] n+ (M = Au, Pd, Pt; x = 0‐2) protected gold superatoms: Insights from relativistic density functional theory calculations
journal, October 2019
- Quintana, Constanza G.; Ocayo, Fernanda; Guajardo Maturana, Raul
- International Journal of Quantum Chemistry, Vol. 120, Issue 2
Recent Advances in Atomic Metal Doping of Carbon-based Nanomaterials for Energy Conversion
journal, April 2017
- Bayatsarmadi, Bita; Zheng, Yao; Vasileff, Anthony
- Small, Vol. 13, Issue 21
The solely motif-doped Au 36−x Ag x (SPh-tBu) 24 (x = 1–8) nanoclusters: X-ray crystal structure and optical properties
journal, January 2016
- Fan, Jiqiang; Song, Yongbo; Chai, Jinsong
- Nanoscale, Vol. 8, Issue 33
The tetrahedral structure and luminescence properties of Bi-metallic Pt 1 Ag 28 (SR) 18 (PPh 3 ) 4 nanocluster
journal, January 2017
- Kang, Xi; Zhou, Meng; Wang, Shuxin
- Chemical Science, Vol. 8, Issue 4
Controlling Ag-doping in [Ag x Au 25−x (SC 6 H 11 ) 18 ] − nanoclusters: cryogenic optical, electronic and electrocatalytic properties
journal, January 2017
- Jin, Renxi; Zhao, Shuo; Liu, Chong
- Nanoscale, Vol. 9, Issue 48
Au 25 (SR) 18 : the captain of the great nanocluster ship
journal, January 2018
- Kang, Xi; Chong, Hanbao; Zhu, Manzhou
- Nanoscale, Vol. 10, Issue 23
New stable isomorphous Ag 34 and Ag 33 Au nanoclusters with an open shell electronic structure
journal, January 2018
- Xi, Xiao-Juan; Yang, Jin-Sen; Wang, Jia-Yin
- Nanoscale, Vol. 10, Issue 45
Triple 1D1D superatomic bonding. Au 22 (dppo) 6 as a Π 4 - and Δ 2 -triply bonded cluster based on Au 11 assembled units
journal, January 2020
- Muñoz-Castro, Alvaro
- Physical Chemistry Chemical Physics, Vol. 22, Issue 3
Distinct photophysical properties in atom-precise silver and copper nanocluster analogues
journal, January 2019
- Li, Yan-Ling; Wang, Zhao-Yang; Ma, Xiao-Hong
- Nanoscale, Vol. 11, Issue 12
Elucidating ligand effects in thiolate-protected metal clusters using Au 24 Pt(TBBT) 18 as a model cluster
journal, January 2019
- Hossain, Sakiat; Imai, Yukari; Suzuki, Daiki
- Nanoscale, Vol. 11, Issue 45
An overview on the current understanding of the photophysical properties of metal nanoclusters and their potential applications
journal, January 2019
- Maity, Subarna; Bain, Dipankar; Patra, Amitava
- Nanoscale, Vol. 11, Issue 47