Analytical Approaches To Identify Plasmon-like Excited States in Bare and Ligand-Protected Metal Nanoclusters

Gieseking, Rebecca L.  M.; Ashwell, Adam P.; Ratner, Mark A.; Schatz, George C.

doi:10.1021/acs.jpcc.9b10569

Title: Analytical Approaches To Identify Plasmon-like Excited States in Bare and Ligand-Protected Metal Nanoclusters

Journal Article · 15 January 2020 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.9b10569 · OSTI ID:1598588

^[1]; Ashwell, Adam P. ^[2];

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^[2]

Brandeis Univ., Waltham, MA (United States)
Northwestern Univ., Evanston, IL (United States)

Noble metal nanoclusters containing dozens to hundreds of metal atoms are of great interest because of their unique optical properties. Classical electrodynamics fails to describe the optical properties of clusters smaller than ~5 nm, so quantum mechanical models are needed to describe these clusters. However, it is challenging to identify which features of the computed excited states indicate plasmon-like character, particularly in a way that is generalizable to the ligand-protected clusters that are commonly studied in experiments. We present an analytical method to identify plasmon-like excited states using three quantifiable indicators that must be considered in combination: (1) large superatomic character, (2) large collectivity among single-particle excitations, and (3) large additivity of contributions of these single-particle excitations to the transition dipole moment. Visualizing these three indicators on a single plot enables rapid classification of hundreds of excited states into plasmon-like, collective, single-particle, or interband categories, or as intermediate between these categories. Lastly, this method is used to identify excited states with plasmon-like character in both bare and ligand-protected Ag clusters at the TDDFT level. Using these three nearly orthogonal indicators in combination provides more information than any one criterion can provide.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0004752

OSTI ID:: 1598588

Journal Information:: Journal of Physical Chemistry. C, Vol. 124, Issue 5; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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References (40)

From Discrete Electronic States to Plasmons: TDDFT Optical Absorption Properties of Ag _n ( n = 10, 20, 35, 56, 84, 120) Tetrahedral Clusters Aikens, Christine M.; Li, Shuzhou; Schatz, George C. The Journal of Physical Chemistry C, Vol. 112, Issue 30 https://doi.org/10.1021/jp802707r	journal	July 2008
Quantum mechanical origin of the plasmon: from molecular systems to nanoparticles Guidez, Emilie B.; Aikens, Christine M. Nanoscale, Vol. 6, Issue 20 https://doi.org/10.1039/C4NR02225D	journal	January 2014
Plasmons in Molecules Bernadotte, Stephan; Evers, Ferdinand; Jacob, Christoph R. The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp3113073	journal	January 2013
Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C. The Journal of Physical Chemistry A, Vol. 120, Issue 26 https://doi.org/10.1021/acs.jpca.6b04520	journal	June 2016
Analysis of Localized Surface Plasmon Resonances in Spherical Jellium Clusters and Their Assemblies Selenius, Elli; Malola, Sami; Häkkinen, Hannu The Journal of Physical Chemistry C, Vol. 121, Issue 48 https://doi.org/10.1021/acs.jpcc.7b10154	journal	November 2017
Plasmonic Resonances in the Al ₁₃ ^– Cluster: Quantification and Origin of Exciton Collectivity Casanova, David; Matxain, Jon M.; Ugalde, Jesus M. The Journal of Physical Chemistry C, Vol. 120, Issue 23 https://doi.org/10.1021/acs.jpcc.6b03210	journal	June 2016
Quantifying the Plasmonic Character of Optical Excitations in Nanostructures Bursi, Luca; Calzolari, Arrigo; Corni, Stefano ACS Photonics, Vol. 3, Issue 4 https://doi.org/10.1021/acsphotonics.5b00688	journal	March 2016
How To Identify Plasmons from the Optical Response of Nanostructures Zhang, Runmin; Bursi, Luca; Cox, Joel D. ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b03421	journal	July 2017
Reversing the size-dependence of surface plasmon resonances Peng, S.; McMahon, J. M.; Schatz, G. C. Proceedings of the National Academy of Sciences, Vol. 107, Issue 33 https://doi.org/10.1073/pnas.1007524107	journal	July 2010
Classical and ab Initio Plasmonics Meet at Sub-nanometric Noble Metal Rods Sinha-Roy, Rajarshi; García-González, Pablo; Weissker, Hans-Christian ACS Photonics, Vol. 4, Issue 6 https://doi.org/10.1021/acsphotonics.7b00254	journal	May 2017
Quantum plasmonic nanoantennas Fitzgerald, Jamie M.; Azadi, Sam; Giannini, Vincenzo Physical Review B, Vol. 95, Issue 23 https://doi.org/10.1103/PhysRevB.95.235414	journal	June 2017
Time-Dependent Density Functional Theory Studies of Optical Properties of Ag Nanoparticles: Octahedra, Truncated Octahedra, and Icosahedra Bae, Gyun-Tack; Aikens, Christine M. The Journal of Physical Chemistry C, Vol. 116, Issue 18 https://doi.org/10.1021/jp300789x	journal	May 2012
All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures Yang, Huayan; Wang, Yu; Huang, Huaqi Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3422	journal	September 2013
[Ag ₂₅ (SR) ₁₈ ] ⁻ : The “Golden” Silver Nanoparticle Joshi, Chakra P.; Bootharaju, Megalamane S.; Alhilaly, Mohammad J. Journal of the American Chemical Society, Vol. 137, Issue 36 https://doi.org/10.1021/jacs.5b07088	journal	September 2015
Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles Chakraborty, Indranath; Pradeep, Thalappil Chemical Reviews, Vol. 117, Issue 12 https://doi.org/10.1021/acs.chemrev.6b00769	journal	June 2017
Designing ligand-enhanced optical absorption of thiolated gold nanoclusters Sementa, L.; Barcaro, G.; Dass, A. Chemical Communications, Vol. 51, Issue 37 https://doi.org/10.1039/C5CC01951F	journal	January 2015
Ligand-Enhanced Optical Response of Gold Nanomolecules and Its Fragment Projection Analysis: The Case of Au ₃₀ (SR) ₁₈ Sementa, Luca; Barcaro, Giovanni; Baseggio, Oscar The Journal of Physical Chemistry C, Vol. 121, Issue 20 https://doi.org/10.1021/acs.jpcc.6b12029	journal	January 2017
Birth of the Localized Surface Plasmon Resonance in Monolayer-Protected Gold Nanoclusters Malola, Sami; Lehtovaara, Lauri; Enkovaara, Jussi ACS Nano, Vol. 7, Issue 11 https://doi.org/10.1021/nn4046634	journal	October 2013
Identification of Plasmons in Molecules with Scaled Ab Initio Approaches Krauter, Caroline M.; Bernadotte, Stephan; Jacob, Christoph R. The Journal of Physical Chemistry C, Vol. 119, Issue 43 https://doi.org/10.1021/acs.jpcc.5b07659	journal	October 2015
Light-Induced Field Enhancement in Nanoscale Systems from First-Principles: The Case of Polyacenes Bursi, Luca; Calzolari, Arrigo; Corni, Stefano ACS Photonics, Vol. 1, Issue 10 https://doi.org/10.1021/ph500269q	journal	September 2014
Interplay between plasmon and single-particle excitations in a metal nanocluster Ma, Jie; Wang, Zhi; Wang, Lin-Wang Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms10107	journal	December 2015
Density-functional approximation for the correlation energy of the inhomogeneous electron gas Perdew, John P. Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8822	journal	June 1986
The zero‐order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules van Lenthe, E.; Snijders, J. G.; Baerends, E. J. The Journal of Chemical Physics, Vol. 105, Issue 15 https://doi.org/10.1063/1.472460	journal	October 1996
Approximation of the exchange-correlation Kohn–Sham potential with a statistical average of different orbital model potentials Gritsenko, O. V.; Schipper, P. R. T.; Baerends, E. J. Chemical Physics Letters, Vol. 302, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)00128-1	journal	March 1999
Chemistry with ADF te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J. Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967 https://doi.org/10.1002/jcc.1056	journal	January 2001
Electronic Shell Structure and Abundances of Sodium Clusters Knight, W. D.; Clemenger, Keith; de Heer, Walt A. Physical Review Letters, Vol. 52, Issue 24 https://doi.org/10.1103/PhysRevLett.52.2141	journal	June 1984
Electronic Structure of Ligand-Passivated Gold and Silver Nanoclusters Aikens, Christine M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 2 https://doi.org/10.1021/jz101499g	journal	December 2010
A unified view of ligand-protected gold clusters as superatom complexes Walter, M.; Akola, J.; Lopez-Acevedo, O. Proceedings of the National Academy of Sciences, Vol. 105, Issue 27 https://doi.org/10.1073/pnas.0801001105	journal	July 2008
Structural Influence on Superatomic Orbitals of Typical Gold Nanostructure Building Blocks Jiang, Wanrun; Gao, Yang; Xu, Dexuan Journal of Electronic Materials, Vol. 46, Issue 7 https://doi.org/10.1007/s11664-016-5006-3	journal	October 2016
[Ag ₆₇ (SPhMe ₂ ) ₃₂ (PPh ₃ ) ₈ ] ³⁺ : Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster Alhilaly, Mohammad J.; Bootharaju, Megalamane S.; Joshi, Chakra P. Journal of the American Chemical Society, Vol. 138, Issue 44 https://doi.org/10.1021/jacs.6b09007	journal	October 2016
Electronic structure of gold, aluminum, and gallium superatom complexes Lopez-Acevedo, O.; Clayborne, P. A.; Häkkinen, H. Physical Review B, Vol. 84, Issue 3 https://doi.org/10.1103/PhysRevB.84.035434	journal	July 2011
Atomic and electronic structure of gold clusters: understanding flakes, cages and superatoms from simple concepts Häkkinen, Hannu Chemical Society Reviews, Vol. 37, Issue 9 https://doi.org/10.1039/b717686b	journal	January 2008
Evidence of superatom electronic shells in ligand-stabilized aluminum clusters Andre Clayborne, P.; Lopez-Acevedo, Olga; Whetten, Robert L. The Journal of Chemical Physics, Vol. 135, Issue 9 https://doi.org/10.1063/1.3632087	journal	September 2011
Quantum coherent plasmon in silver nanowires: A real-time TDDFT study Ding, Feizhi; Guidez, Emilie B.; Aikens, Christine M. The Journal of Chemical Physics, Vol. 140, Issue 24 https://doi.org/10.1063/1.4884388	journal	June 2014
Plasmon resonances in linear atomic chains: Free-electron behavior and anisotropic screening of d electrons Yan, Jun; Gao, Shiwu Physical Review B, Vol. 78, Issue 23 https://doi.org/10.1103/PhysRevB.78.235413	journal	December 2008
Third-Order Nonlinear Optical Properties of Ag Nanoclusters: Connecting Molecule-like and Nanoparticle-like Behavior Gieseking, Rebecca L. M. Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.9b01290	journal	December 2018
Quantum Mechanical Identification of Quadrupolar Plasmonic Excited States in Silver Nanorods Gieseking, Rebecca L.; Ratner, Mark A.; Schatz, George C. The Journal of Physical Chemistry A, Vol. 120, Issue 46 https://doi.org/10.1021/acs.jpca.6b09649	journal	November 2016
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
Ultrastable silver nanoparticles Desireddy, Anil; Conn, Brian E.; Guo, Jingshu Nature, Vol. 501, Issue 7467 https://doi.org/10.1038/nature12523	journal	September 2013
Plasmon Excitations in Mixed Metallic Nanoarrays Conley, Kevin M.; Nayyar, Neha; Rossi, Tuomas P. ACS Nano, Vol. 13, Issue 5 https://doi.org/10.1021/acsnano.8b09826	journal	April 2019

Cited By (1)

Plasmon excitations in chemically heterogeneous nanoarrays Conley, Kevin; Nayyar, Neha; Rossi, Tuomas P. Physical Review B, Vol. 101, Issue 23 https://doi.org/10.1103/physrevb.101.235132	journal	June 2020

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