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

Title: Theoretical Insights into the Origin of Photoluminescence of Au25(SR)18– Nanoparticles

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b05293· OSTI ID:1366552
 [1];  [1]
  1. Department of Chemistry, Kansas State University, Manhattan, Kansas 66506, United States
+ Show Author Affiliations

Understanding fundamental behavior of luminescent nanomaterials upon photoexcitation is necessary to expand photocatalytic and biological imaging applications. Despite the significant amount of experimental work into the luminescence of Au25(SR)18– clusters, the origin of photoluminescence in these clusters still remains unclear. In this study, the geometric and electronic structural changes of the Au25(SR)18– (R = H, CH3, CH2CH3, CH2CH2CH3) nanoclusters upon photoexcitation are discussed using time-dependent density functional theory (TD-DFT) methods. Geometric relaxations in the optimized excited states of up to 0.33 Å impart remarkable effects on the energy levels of the frontier orbitals of Au25(SR)18– nanoclusters. This gives rise to a Stokes shift of 0.49 eV for Au25(SH)18– in agreement with experiments. Even larger Stokes shifts are predicted for longer ligands. Vibrational frequencies in the 75–80 cm–1 range are calculated for the nuclear motion involved in the excited-state nuclear relaxation; this value is in excellent agreement with vibrational beating observed in time-resolved spectroscopy experiments. Several excited states around 0.8, 1.15, and 1.25 eV are calculated for the Au25(SH)18– nanocluster. Considering the typical underestimation of DFT excitation energies, these states are likely responsible for the emission observed experimentally in the 1.15–1.55 eV range. In conclusion, all excited states arise from core-based orbitals; charge-transfer states or other “semi-ring” or ligand-based states are not implicated.

Research Organization:
Kansas State Univ., Manhattan, KS (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012273
OSTI ID:
1366552
Alternate ID(s):
OSTI ID: 1436125
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 35; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 164 works
Citation information provided by
Web of Science

References (55)

Photoluminescence from nanosize gold clusters journal June 1998
Origin of Discrete Optical Absorption Spectra of M 25 (SH) 18 − Nanoparticles (M = Au, Ag) journal November 2008
Nonscalable Oxidation Catalysis of Gold Clusters journal December 2013
Different sized luminescent gold nanoparticles journal January 2012
Magic-Numbered Au n Clusters Protected by Glutathione Monolayers ( n = 18, 21, 25, 28, 32, 39):  Isolation and Spectroscopic Characterization journal June 2004
Electronic Structure of Ligand-Passivated Gold and Silver Nanoclusters journal December 2010
Transition from nanoparticle to molecular behavior: a femtosecond transient absorption study of a size-selected 28 atom gold cluster journal April 2002
Protein-Directed Synthesis of Highly Fluorescent Gold Nanoclusters journal January 2009
Jahn–Teller effects in Au 25 (SR) 18 journal January 2016
A unified view of ligand-protected gold clusters as superatom complexes journal July 2008
Near-Infrared Luminescence from Small Gold Nanocrystals journal August 2000
Identification of a Highly Luminescent Au 22 (SG) 18 Nanocluster journal January 2014
Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm Regime journal December 2010
On the Structure of Thiolate-Protected Au 25 journal March 2008
Electrochemistry and Optical Absorbance and Luminescence of Molecule-like Au 38 Nanoparticles journal May 2004
On the Ligand’s Role in the Fluorescence of Gold Nanoclusters journal July 2010
Glutathione-Protected Gold Clusters Revisited:  Bridging the Gap between Gold(I)−Thiolate Complexes and Thiolate-Protected Gold Nanocrystals journal April 2005
Chemistry with ADF journal January 2001
Titania supported gold nanoparticles as photocatalyst journal January 2011
Giant Gold−Glutathione Cluster Compounds:  Intense Optical Activity in Metal-Based Transitions journal March 2000
From Discrete Electronic States to Plasmons: TDDFT Optical Absorption Properties of Ag n ( n = 10, 20, 35, 56, 84, 120) Tetrahedral Clusters journal July 2008
Gold Nanomaterials at Work in Biomedicine journal April 2015
Ultrafast Relaxation Dynamics of [Au 25 (SR) 18 ] q Nanoclusters: Effects of Charge State journal November 2010
Structure, Bonding, and Linear Optical Properties of a Series of Silver and Gold Nanorod Clusters: DFT/TDDFT Studies journal December 2010
Macmolplt: a graphical user interface for GAMESS journal June 1998
Quantum-Sized Gold Clusters as Efficient Two-Photon Absorbers journal April 2008
Unique Ultrafast Visible Luminescence in Monolayer-Protected Au 25 Clusters journal December 2010
Near-IR Luminescence of Monolayer-Protected Metal Clusters journal January 2005
Visible Luminescence of Water-Soluble Monolayer-Protected Gold Clusters journal December 2001
Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation journal January 2013
Visible-light photocatalytic activity of gold nanoparticles supported on template-synthesized mesoporous titania for the decontamination of the chemical warfare agent Soman journal August 2010
The Structure and Optical Properties of the [Au 18 (SR) 14 ] Nanocluster journal January 2015
A simple model for understanding the fluorescence behavior of Au25 nanoclusters journal January 2014
Time-Dependent Density Functional Theory Study of the Luminescence Properties of Gold Phosphine Thiolate Complexes journal March 2015
Efficient Visible-Light-Induced Photocatalytic Activity on Gold-Nanoparticle-Supported Layered Titanate journal December 2010
Visible to Infrared Luminescence from a 28-Atom Gold Cluster journal April 2002
Ultrafast Optical Study of Small Gold Monolayer Protected Clusters: A Closer Look at Emission journal May 2010
Time-Dependent Density Functional Theory Studies of Optical Properties of Au Nanoparticles: Octahedra, Truncated Octahedra, and Icosahedra journal September 2015
Assessment of exchange-correlation functionals for the calculation of dynamical properties of small clusters in time-dependent density functional theory journal August 2001
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
The `lightning' gold nanorods: fluorescence enhancement of over a million compared to the gold metal journal February 2000
Femtosecond Relaxation Dynamics of Au 25 L 18 − Monolayer-Protected Clusters journal May 2009
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
Electronic and Vibrational Signatures of the Au 102 ( p -MBA) 44 Cluster journal March 2011
New Gold Nanostructures for Sensor Applications: A Review journal July 2014
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
Effects of Core Distances, Solvent, Ligand, and Level of Theory on the TDDFT Optical Absorption Spectrum of the Thiolate-Protected Au 25 Nanoparticle journal October 2009
PHOTOLUMINESCENCE AND TEMPERATURE-DEPENDENT EMISSION STUDIES OF Au 25 CLUSTERS IN THE SOLID STATE journal February 2009
Crystal Structure of the Gold Nanoparticle [N(C 8 H 17 ) 4 ][Au 25 (SCH 2 CH 2 Ph) 18 ] journal March 2008
Photoluminescence of Metals journal February 1969
Ligand Exchange of Au 25 SG 18 Leading to Functionalized Gold Clusters: Spectroscopy, Kinetics, and Luminescence journal July 2008
Isolation and Selected Properties of a 10.4 kDa Gold:Glutathione Cluster Compound journal December 1998
Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation journal September 2008
NIR Luminescence Intensities Increase Linearly with Proportion of Polar Thiolate Ligands in Protecting Monolayers of Au 38 and Au 140 Quantum Dots journal October 2006
A DFT and MP2 study of luminescence of gold(I) complexes journal August 2006

Figures / Tables (12)

Figure 1(p. 2)figure Figure 1
Table 1(p. 3)table Table 1
Table 2(p. 3)table Table 2
Figure 2(p. 4)figure Figure 2
Figure 3(p. 4)figure Figure 3
Table 3(p. 5)table Table 3
Table 4(p. 5)table Table 4
Figure 4(p. 6)figure Figure 4
Table 5(p. 6)table Table 5
Table 6(p. 6)table Table 6
Figure 5(p. 7)figure Figure 5
Table 7(p. 7)table Table 7

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY