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Title: Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation

Abstract

In solid state physics, electronic excitations are often classified as plasmons or single-particle excitations. The former class of states refers to collective oscillations of the electron density. The random-phase approximation allows for a quantum-theoretical treatment and a characterization on a microscopic level as a coherent superposition of a large number of particle-hole transitions with the same momentum transfer. However, small systems such as molecules or small nanoclusters lack the basic properties (momentum conservation and uniform exchange interaction) responsible for the formation of plasmons in the solid-state case. Despite an enhanced interest in plasmon-based technologies and an increasing number of studies regarding plasmons in molecules and small nanoclusters, their definition on a microscopic level of theory remains ambiguous. In this work, we analyze the microscopic properties of molecular plasmons in comparison with the homogeneous electron gas as a model system. Subsequently, the applicability of the derived characteristics is validated by analyzing the electronic excitation vectors with respect to orbital transitions for two linear polyenes within second order versions of the algebraic diagrammatic construction scheme for the polarization propagator.

Authors:
 [1];  [2]; ;  [1];  [3];  [4]
  1. Theoretical Chemistry, Heidelberg University, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)
  2. (Germany)
  3. Center for Functional Nanostructures and Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Wolfgang-Gaede-Strasse 1a, 76131 Karlsruhe (Germany)
  4. Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)
Publication Date:
OSTI Identifier:
22308356
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRON GAS; EXCITATION; MOLECULES; MOMENTUM TRANSFER; NANOSTRUCTURES; OSCILLATIONS; PARTICLES; PLASMONS; POLARIZATION; POLYENES; RANDOM PHASE APPROXIMATION; SOLIDS

Citation Formats

Krauter, Caroline M., E-mail: Caroline.Krauter@pci.uni-heidelberg.de, Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, 69120 Heidelberg, Schirmer, Jochen, Pernpointner, Markus, Jacob, Christoph R., and Dreuw, Andreas. Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation. United States: N. p., 2014. Web. doi:10.1063/1.4894266.
Krauter, Caroline M., E-mail: Caroline.Krauter@pci.uni-heidelberg.de, Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, 69120 Heidelberg, Schirmer, Jochen, Pernpointner, Markus, Jacob, Christoph R., & Dreuw, Andreas. Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation. United States. doi:10.1063/1.4894266.
Krauter, Caroline M., E-mail: Caroline.Krauter@pci.uni-heidelberg.de, Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, 69120 Heidelberg, Schirmer, Jochen, Pernpointner, Markus, Jacob, Christoph R., and Dreuw, Andreas. Sun . "Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation". United States. doi:10.1063/1.4894266.
@article{osti_22308356,
title = {Plasmons in molecules: Microscopic characterization based on orbital transitions and momentum conservation},
author = {Krauter, Caroline M., E-mail: Caroline.Krauter@pci.uni-heidelberg.de and Interdisciplinary Center for Scientific Computing, Heidelberg University, Im Neuenheimer Feld 368, 69120 Heidelberg and Schirmer, Jochen and Pernpointner, Markus and Jacob, Christoph R. and Dreuw, Andreas},
abstractNote = {In solid state physics, electronic excitations are often classified as plasmons or single-particle excitations. The former class of states refers to collective oscillations of the electron density. The random-phase approximation allows for a quantum-theoretical treatment and a characterization on a microscopic level as a coherent superposition of a large number of particle-hole transitions with the same momentum transfer. However, small systems such as molecules or small nanoclusters lack the basic properties (momentum conservation and uniform exchange interaction) responsible for the formation of plasmons in the solid-state case. Despite an enhanced interest in plasmon-based technologies and an increasing number of studies regarding plasmons in molecules and small nanoclusters, their definition on a microscopic level of theory remains ambiguous. In this work, we analyze the microscopic properties of molecular plasmons in comparison with the homogeneous electron gas as a model system. Subsequently, the applicability of the derived characteristics is validated by analyzing the electronic excitation vectors with respect to orbital transitions for two linear polyenes within second order versions of the algebraic diagrammatic construction scheme for the polarization propagator.},
doi = {10.1063/1.4894266},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}