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Title: Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation

Abstract

Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to the transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. Furthermore, these results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficientmore » to describe the optical spectra of plasmonic excitations quantum mechanically.« less

Authors:
 [1];  [1];  [1]
  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1258703
Alternate Identifier(s):
OSTI ID: 1268309
Grant/Contract Number:  
FG02-10ER16153
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Volume: 120 Journal Issue: 26; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Gieseking, Rebecca L., Ratner, Mark A., and Schatz, George C. Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b04520.
Gieseking, Rebecca L., Ratner, Mark A., & Schatz, George C. Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation. United States. https://doi.org/10.1021/acs.jpca.6b04520
Gieseking, Rebecca L., Ratner, Mark A., and Schatz, George C. Thu . "Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation". United States. https://doi.org/10.1021/acs.jpca.6b04520.
@article{osti_1258703,
title = {Semiempirical Modeling of Ag Nanoclusters: New Parameters for Optical Property Studies Enable Determination of Double Excitation Contributions to Plasmonic Excitation},
author = {Gieseking, Rebecca L. and Ratner, Mark A. and Schatz, George C.},
abstractNote = {Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to the transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. Furthermore, these results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficient to describe the optical spectra of plasmonic excitations quantum mechanically.},
doi = {10.1021/acs.jpca.6b04520},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 26,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.6b04520

Citation Metrics:
Cited by: 14 works
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Works referenced in this record:

Time-Dependent Density Functional Theory Studies of Optical Properties of Ag Nanoparticles: Octahedra, Truncated Octahedra, and Icosahedra
journal, May 2012

  • Bae, Gyun-Tack; Aikens, Christine M.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 18
  • DOI: 10.1021/jp300789x

Electromagnetic fields around silver nanoparticles and dimers
journal, January 2004

  • Hao, Encai; Schatz, George C.
  • The Journal of Chemical Physics, Vol. 120, Issue 1, p. 357-366
  • DOI: 10.1063/1.1629280

Electronic structure methods for studying surface-enhanced Raman scattering
journal, January 2008

  • Jensen, Lasse; Aikens, Christine M.; Schatz, George C.
  • Chemical Society Reviews, Vol. 37, Issue 5
  • DOI: 10.1039/b706023h

Exchange-correlation potential with correct asymptotic behavior
journal, April 1994


The Optical Properties of Metal Nanoparticles:  The Influence of Size, Shape, and Dielectric Environment
journal, January 2003

  • Kelly, K. Lance; Coronado, Eduardo; Zhao, Lin Lin
  • The Journal of Physical Chemistry B, Vol. 107, Issue 3
  • DOI: 10.1021/jp026731y

Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation
journal, September 2014

  • Krauter, Caroline M.; Schirmer, Jochen; Jacob, Christoph R.
  • The Journal of Chemical Physics, Vol. 141, Issue 10
  • DOI: 10.1063/1.4894266

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


Optical electric-field enhancement at a metal surface arising from surface-plasmon excitation
journal, January 1981


QM/MM Study of Photoinduced Reduction of a Tetrahedral Ag 20 + Cluster by a Ag Atom
journal, December 2012

  • Chen, Hanning; Ratner, Mark A.; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 4
  • DOI: 10.1021/jp310149y

Theoretical analysis of the optical excitation spectra of silver and gold nanowires
journal, January 2012

  • Guidez, Emilie B.; Aikens, Christine M.
  • Nanoscale, Vol. 4, Issue 14
  • DOI: 10.1039/c2nr30253e

Time-Dependent Theory of the Rate of Photo-induced Electron Transfer
journal, September 2011

  • Chen, Hanning; Ratner, Mark A.; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 38
  • DOI: 10.1021/jp205262u

Size-Dependence of the Enhanced Raman Scattering of Pyridine Adsorbed on Ag n ( n = 2−8, 20) Clusters
journal, March 2007

  • Jensen, Lasse; Zhao, Lin Lin; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 12
  • DOI: 10.1021/jp067634y

Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986


Island size effects in nanoparticle-enhanced photodetectors
journal, December 1998

  • Stuart, Howard R.; Hall, Dennis G.
  • Applied Physics Letters, Vol. 73, Issue 26
  • DOI: 10.1063/1.122903

Plasmons in Molecules
journal, January 2013

  • Bernadotte, Stephan; Evers, Ferdinand; Jacob, Christoph R.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 4
  • DOI: 10.1021/jp3113073

Origin and TDDFT Benchmarking of the Plasmon Resonance in Acenes
journal, October 2013

  • Guidez, Emilie B.; Aikens, Christine M.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 41
  • DOI: 10.1021/jp4059033

Surface plasmon enhanced silicon solar cells
journal, May 2007

  • Pillai, S.; Catchpole, K. R.; Trupke, T.
  • Journal of Applied Physics, Vol. 101, Issue 9
  • DOI: 10.1063/1.2734885

Quantum mechanical origin of the plasmon: from molecular systems to nanoparticles
journal, January 2014

  • Guidez, Emilie B.; Aikens, Christine M.
  • Nanoscale, Vol. 6, Issue 20
  • DOI: 10.1039/C4NR02225D

TDDFT and CIS Studies of Optical Properties of Dimers of Silver Tetrahedra
journal, July 2012

  • Bae, Gyun-Tack; Aikens, Christine M.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 31
  • DOI: 10.1021/jp305330e

Single Molecule Detection Using Surface-Enhanced Raman Scattering (SERS)
journal, March 1997


The zero‐order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules
journal, October 1996

  • van Lenthe, E.; Snijders, J. G.; Baerends, E. J.
  • The Journal of Chemical Physics, Vol. 105, Issue 15
  • DOI: 10.1063/1.472460

Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

TDDFT Studies of Absorption and SERS Spectra of Pyridine Interacting with Au 20
journal, December 2006

  • Aikens, Christine M.; Schatz, George C.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 49
  • DOI: 10.1021/jp065206m

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

  • Aikens, Christine M.; Li, Shuzhou; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 30
  • DOI: 10.1021/jp802707r

Surface-enhanced Raman spectroscopy: a brief retrospective
journal, January 2005

  • Moskovits, Martin
  • Journal of Raman Spectroscopy, Vol. 36, Issue 6-7
  • DOI: 10.1002/jrs.1362

Determination of one-centre core integrals from the average energies of atomic configurations
journal, January 1973

  • Karlsson, G�ran; Zerner, Michael C.
  • International Journal of Quantum Chemistry, Vol. 7, Issue 1
  • DOI: 10.1002/qua.560070106

Design of Gold Nanoparticle-Based Colorimetric Biosensing Assays
journal, October 2008

  • Zhao, Weian; Brook, Michael A.; Li, Yingfu
  • ChemBioChem, Vol. 9, Issue 15, p. 2363-2371
  • DOI: 10.1002/cbic.200800282

Towards an order-
journal, January 1998

  • Fonseca Guerra, C.; Snijders, J. G.; te Velde, G.
  • Theoretical Chemistry Accounts, Vol. 99, Issue 6
  • DOI: 10.1007/s002140050021

Identification of Plasmons in Molecules with Scaled Ab Initio Approaches
journal, October 2015

  • Krauter, Caroline M.; Bernadotte, Stephan; Jacob, Christoph R.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 43
  • DOI: 10.1021/acs.jpcc.5b07659

Spectral Properties and Relaxation Dynamics of Surface Plasmon Electronic Oscillations in Gold and Silver Nanodots and Nanorods
journal, October 1999

  • Link, Stephan; El-Sayed, Mostafa A.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 40
  • DOI: 10.1021/jp9917648

INDO/S parameters for gold
journal, January 2002

  • Shapley, Warwick A.; Reimers, Jeffrey R.; Hush, Noel S.
  • International Journal of Quantum Chemistry, Vol. 90, Issue 1
  • DOI: 10.1002/qua.10058

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Biosensing with plasmonic nanosensors
journal, June 2008

  • Anker, Jeffrey N.; Hall, W. Paige; Lyandres, Olga
  • Nature Materials, Vol. 7, Issue 6
  • DOI: 10.1038/nmat2162

Perspectives on double-excitations in TDDFT
journal, November 2011


MOPAC: A semiempirical molecular orbital program
journal, March 1990

  • Stewart, James J. P.
  • Journal of Computer-Aided Molecular Design, Vol. 4, Issue 1
  • DOI: 10.1007/BF00128336

Localized Surface Plasmon Resonance Spectroscopy and Sensing
journal, May 2007


Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering
journal, February 1997


Approximation of the exchange-correlation Kohn–Sham potential with a statistical average of different orbital model potentials
journal, March 1999


An intermediate neglect of differential overlap model for second-row transition metal species
journal, January 1991

  • Anderson, Wayne P.; Cundari, Thomas R.; Zerner, Michael C.
  • International Journal of Quantum Chemistry, Vol. 39, Issue 1
  • DOI: 10.1002/qua.560390106

Plasmon resonance analysis with configuration interaction
journal, January 2014

  • Guidez, Emilie B.; Aikens, Christine M.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 29
  • DOI: 10.1039/c4cp01365d

Potential-energy surfaces of local excited states from subsystem- and selective Kohn–Sham-TDDFT
journal, November 2011