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Title: Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

Journal Article · · Nanoscale
DOI: https://doi.org/10.1039/c6nr01008c · OSTI ID:1326756
 [1];  [1];  [2];  [3];  [1]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Institute for Molecular Science, Myodaiji (Japan); Kyoto Univ., Kyoto (Japan)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI ID:
1326756
Report Number(s):
BNL--112653-2016-JA; KC0403020
Journal Information:
Nanoscale, Journal Name: Nanoscale Journal Issue: 13 Vol. 8; ISSN NANOHL; ISSN 2040-3364
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
Center for Functional Nanomaterials
doped nanoclusters
electronic properties
excited state dynamics
transient absorption