Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au 25 (SH) 18 ] − clusters
Abstract
Nanoscale gold clusters exhibit unique electronic and optical properties. Here, we study the excited state dynamics and electron–phonon coupling of [Au 25 (SH) 18 ] – nanoclusters by using quantum‐classical molecular dynamics combined with time‐dependent density‐functional theory. Our result reproduces the experimental measurements and provides further insights into the relaxation dynamics of ligand protected gold clusters. We examine the ultrafast electronic dynamics induced by specific phonon modes. The roles of the Au 13 core and Au 12 ring in the optical process are investigated. We find that the LUMO–HOMO transition is dominated by AuAu stretching of the Au 13 core, whereas the LUMO + 1 − HOMO transition is induced by breathing vibrations of the Au core as well as AuS stretching. We clarify the interplay between electron–phonon couplings and specific energy‐transfer processes in [Au 25 (SH) 18 ] – nanoclusters.
- Authors:
-
- Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon‐Based Functional Materials and Devices Soochow University Suzhou Jiangsu 215123 P.R. China
- Department of Chemistry University of Southern California Los Angeles CA 90089 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1401163
- Grant/Contract Number:
- DE‐SC0014429
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Physica Status Solidi B. Basic Solid State Physics
- Additional Journal Information:
- Journal Name: Physica Status Solidi B. Basic Solid State Physics Journal Volume: 253 Journal Issue: 3; Journal ID: ISSN 0370-1972
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Chen, Xue, Prezhdo, Oleg V., Ma, Zeyao, Hou, Tingjun, Guo, Zhenyu, and Li, Youyong. Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au 25 (SH) 18 ] − clusters. Germany: N. p., 2015.
Web. doi:10.1002/pssb.201552405.
Chen, Xue, Prezhdo, Oleg V., Ma, Zeyao, Hou, Tingjun, Guo, Zhenyu, & Li, Youyong. Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au 25 (SH) 18 ] − clusters. Germany. https://doi.org/10.1002/pssb.201552405
Chen, Xue, Prezhdo, Oleg V., Ma, Zeyao, Hou, Tingjun, Guo, Zhenyu, and Li, Youyong. Mon .
"Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au 25 (SH) 18 ] − clusters". Germany. https://doi.org/10.1002/pssb.201552405.
@article{osti_1401163,
title = {Ab initio phonon‐coupled nonadiabatic relaxation dynamics of [Au 25 (SH) 18 ] − clusters},
author = {Chen, Xue and Prezhdo, Oleg V. and Ma, Zeyao and Hou, Tingjun and Guo, Zhenyu and Li, Youyong},
abstractNote = {Nanoscale gold clusters exhibit unique electronic and optical properties. Here, we study the excited state dynamics and electron–phonon coupling of [Au 25 (SH) 18 ] – nanoclusters by using quantum‐classical molecular dynamics combined with time‐dependent density‐functional theory. Our result reproduces the experimental measurements and provides further insights into the relaxation dynamics of ligand protected gold clusters. We examine the ultrafast electronic dynamics induced by specific phonon modes. The roles of the Au 13 core and Au 12 ring in the optical process are investigated. We find that the LUMO–HOMO transition is dominated by AuAu stretching of the Au 13 core, whereas the LUMO + 1 − HOMO transition is induced by breathing vibrations of the Au core as well as AuS stretching. We clarify the interplay between electron–phonon couplings and specific energy‐transfer processes in [Au 25 (SH) 18 ] – nanoclusters.},
doi = {10.1002/pssb.201552405},
journal = {Physica Status Solidi B. Basic Solid State Physics},
number = 3,
volume = 253,
place = {Germany},
year = {Mon Oct 26 00:00:00 EDT 2015},
month = {Mon Oct 26 00:00:00 EDT 2015}
}
https://doi.org/10.1002/pssb.201552405
Web of Science
Works referenced in this record:
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
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Origin of Discrete Optical Absorption Spectra of M 25 (SH) 18 − Nanoparticles (M = Au, Ag)
journal, November 2008
- Aikens, Christine M.
- The Journal of Physical Chemistry C, Vol. 112, Issue 50
Quantum Sized Gold Nanoclusters with Atomic Precision
journal, June 2012
- Qian, Huifeng; Zhu, Manzhou; Wu, Zhikun
- Accounts of Chemical Research, Vol. 45, Issue 9
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Interrogating Near-Infrared Electrogenerated Chemiluminescence of Au 25 (SC 2 H 4 Ph) 18 + Clusters
journal, September 2012
- Swanick, Kalen N.; Hesari, Mahdi; Workentin, Mark S.
- Journal of the American Chemical Society, Vol. 134, Issue 37
Electronic Structure of Ligand-Passivated Gold and Silver Nanoclusters
journal, December 2010
- Aikens, Christine M.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 2
Formation of LiBH4 hydrate with dihydrogen bonding
journal, November 2012
- Yamawaki, Hiroshi; Fujihisa, Hiroshi; Gotoh, Yoshito
- Journal of Alloys and Compounds, Vol. 541
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
Trajectory Surface Hopping in the Time-Dependent Kohn-Sham Approach for Electron-Nuclear Dynamics
journal, October 2005
- Craig, Colleen F.; Duncan, Walter R.; Prezhdo, Oleg V.
- Physical Review Letters, Vol. 95, Issue 16
A unified view of ligand-protected gold clusters as superatom complexes
journal, July 2008
- Walter, M.; Akola, J.; Lopez-Acevedo, O.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 27
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
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
Molecule design and isomorphism synthesis towards artificial enzymes
journal, January 2013
- Zhang, Weisong; Gong, Jingjing; Kang, Zhenhui
- CrystEngComm, Vol. 15, Issue 4
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
Interlocked Catenane-Like Structure Predicted in Au 24 (SR) 20 : Implication to Structural Evolution of Thiolated Gold Clusters from Homoleptic Gold(I) Thiolates to Core-Stacked Nanoparticles
journal, February 2012
- Pei, Yong; Pal, Rhitankar; Liu, Chunyan
- Journal of the American Chemical Society, Vol. 134, Issue 6
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
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
- Green, Thomas D.; Yi, Chongyue; Zeng, Chenjie
- The Journal of Physical Chemistry A, Vol. 118, Issue 45
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
The Story of a Monodisperse Gold Nanoparticle: Au 25 L 18
journal, September 2010
- Parker, Joseph F.; Fields-Zinna, Christina A.; Murray, Royce W.
- Accounts of Chemical Research, Vol. 43, Issue 9
Crystal Structure of the Gold Nanoparticle [N(C 8 H 17 ) 4 ][Au 25 (SCH 2 CH 2 Ph) 18 ]
journal, March 2008
- Heaven, Michael W.; Dass, Amala; White, Peter S.
- Journal of the American Chemical Society, Vol. 130, Issue 12
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
Molecular dynamics with electronic transitions
journal, July 1990
- Tully, John C.
- The Journal of Chemical Physics, Vol. 93, Issue 2
Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters
journal, March 2010
- Lopez-Acevedo, Olga; Kacprzak, Katarzyna A.; Akola, Jaakko
- Nature Chemistry, Vol. 2, Issue 4
Experimental and Computational Investigation of Au 25 Clusters and CO 2 : A Unique Interaction and Enhanced Electrocatalytic Activity
journal, June 2012
- Kauffman, Douglas R.; Alfonso, Dominic; Matranga, Christopher
- Journal of the American Chemical Society, Vol. 134, Issue 24
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138