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Title: New tools for the systematic analysis and visualization of electronic excitations. II. Applications

Abstract

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.

Authors:
; ; ;  [1]
  1. Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)
Publication Date:
OSTI Identifier:
22308986
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; CATIONS; DENSITY MATRIX; EIGENVECTORS; ELECTRONS; EXCITATION; EXCITED STATES; IRIDIUM COMPLEXES; MOLECULES; PYRIDINE; RADICALS; RESONANCE; SPIN ORIENTATION

Citation Formats

Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Bäppler, Stefanie A., Wormit, Michael, and Dreuw, Andreas. New tools for the systematic analysis and visualization of electronic excitations. II. Applications. United States: N. p., 2014. Web. doi:10.1063/1.4885820.
Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Bäppler, Stefanie A., Wormit, Michael, & Dreuw, Andreas. New tools for the systematic analysis and visualization of electronic excitations. II. Applications. United States. doi:10.1063/1.4885820.
Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Bäppler, Stefanie A., Wormit, Michael, and Dreuw, Andreas. Mon . "New tools for the systematic analysis and visualization of electronic excitations. II. Applications". United States. doi:10.1063/1.4885820.
@article{osti_22308986,
title = {New tools for the systematic analysis and visualization of electronic excitations. II. Applications},
author = {Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de and Bäppler, Stefanie A. and Wormit, Michael and Dreuw, Andreas},
abstractNote = {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.},
doi = {10.1063/1.4885820},
journal = {Journal of Chemical Physics},
number = 2,
volume = 141,
place = {United States},
year = {Mon Jul 14 00:00:00 EDT 2014},
month = {Mon Jul 14 00:00:00 EDT 2014}
}