The excited states of a diverse set of molecules are examined using a collection of newly implemented analysis methods. These examples expose the particular power of three of these tools: (i) natural difference orbitals (the eigenvectors of the difference density matrix) for the description of orbital relaxation effects, (ii) analysis of the one-electron transition density matrix in terms of an electron-hole picture to identify charge resonance and excitonic correlation effects, and (iii) state-averaged natural transition orbitals for a compact simultaneous representation of several states. Furthermore, the utility of a wide array of additional analysis methods is highlighted. Five molecules with diverse excited state characteristics are chosen for these tasks: pyridine as a prototypical small heteroaromatic molecule, a model system of six neon atoms to study charge resonance effects, hexatriene in its neutral and radical cation forms to exemplify the cases of double excitations and spin-polarization, respectively, and a model iridium complex as a representative metal organic compound. Using these examples a number of phenomena, which are at first sight unexpected, are highlighted and their physical significance is discussed. Moreover, the generality of the conclusions of this paper is verified by a comparison of single- and multireference ab initio methods.
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14 July 2014
Research Article|
July 10 2014
New tools for the systematic analysis and visualization of electronic excitations. II. Applications
Felix Plasser;
Felix Plasser
a)
Interdisciplinary Center for Scientific Computing,
Ruprecht-Karls-University
, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
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Stefanie A. Bäppler;
Stefanie A. Bäppler
Interdisciplinary Center for Scientific Computing,
Ruprecht-Karls-University
, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
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Michael Wormit;
Michael Wormit
Interdisciplinary Center for Scientific Computing,
Ruprecht-Karls-University
, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
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Andreas Dreuw
Andreas Dreuw
Interdisciplinary Center for Scientific Computing,
Ruprecht-Karls-University
, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
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a)
Electronic mail: [email protected]. URL: http://www.iwr.uni-heidelberg.de/groups/compchem/
J. Chem. Phys. 141, 024107 (2014)
Article history
Received:
May 10 2014
Accepted:
June 18 2014
Connected Content
This is a companion to:
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism
Citation
Felix Plasser, Stefanie A. Bäppler, Michael Wormit, Andreas Dreuw; New tools for the systematic analysis and visualization of electronic excitations. II. Applications. J. Chem. Phys. 14 July 2014; 141 (2): 024107. https://doi.org/10.1063/1.4885820
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