Identification of plasmons in molecules with scaled ab initio approaches

• Verfasst von: Krauter, Caroline M. [VerfasserIn]
• Verfasst von: Pernpointner, Markus [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Identification of plasmons in molecules with scaled ab initio approaches
• Verf.angabe: Caroline M. Krauter, Stephan Bernadotte, Christoph R. Jacob, Markus Pernpointner, and Andreas Dreuw
• Umfang: 10 S.
• Fussnoten: Gesehen am 13.12.2017
• Titel Quelle: Enthalten in: The journal of physical chemistry <Washington, DC> / C
• Jahr Quelle: 2015
• Band/Heft Quelle: 119(2015), 43, S. 24564-24573
• ISSN Quelle: 1932-7455
• DOI: doi:10.1021/acs.jpcc.5b07659
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1566331889

Abstract

For the electronic excitations in metallic systems under periodic boundary conditions, momentum conservation and a uniform electron-electron interaction imply a clear distinction of plasmons and single-particle excitations. For finite molecular systems, this distinction is less clear, but excitations formed by a coherent superposition of elementary particle-hole transitions that show a collective oscillation of the transition electron density have nevertheless been identified as plasmons in molecules. To aid this distinction, a scaling approach [Bernadotte, S.; Evers, F.; Jacob, C. R. J. Phys. Chem. C 2013, 117, 1863] has recently been developed that is based on the observation that, in contrast to single-particle excitations, plasmonic excitation energies strongly depend on the electron-electron interaction. In this work, we adapt the proposed scaling scheme to ab initio models, specifically configuration interaction singles and the second-order algebraic diagrammatic construction scheme of the polarization propagator. The resulting approach is applied to a series of linear polyenes and the characterization based on the scaling method is confirmed by inspection of the eigenvector components, transition density patterns, and transition strengths.