A variety of density matrix based methods for the analysis and visualization of electronic excitations are discussed and their implementation within the framework of the algebraic diagrammatic construction of the polarization propagator is reported. Their mathematical expressions are given and an extensive phenomenological discussion is provided to aid the interpretation of the results. Starting from several standard procedures, e.g., population analysis, natural orbital decomposition, and density plotting, we proceed to more advanced concepts of natural transition orbitals and attachment/detachment densities. In addition, special focus is laid on information coded in the transition density matrix and its phenomenological analysis in terms of an electron-hole picture. Taking advantage of both the orbital and real space representations of the density matrices, the physical information in these analysis methods is outlined, and similarities and differences between the approaches are highlighted. Moreover, new analysis tools for excited states are introduced including state averaged natural transition orbitals, which give a compact description of a number of states simultaneously, and natural difference orbitals (defined as the eigenvectors of the difference density matrix), which reveal details about orbital relaxation effects.
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14 July 2014
Research Article|
July 10 2014
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism
Felix Plasser;
Felix Plasser
a)
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, 024106 (2014)
Article history
Received:
March 15 2014
Accepted:
June 18 2014
Connected Content
A companion article has been published:
New tools for the systematic analysis and visualization of electronic excitations. II. Applications
Citation
Felix Plasser, Michael Wormit, Andreas Dreuw; New tools for the systematic analysis and visualization of electronic excitations. I. Formalism. J. Chem. Phys. 14 July 2014; 141 (2): 024106. https://doi.org/10.1063/1.4885819
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