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Please use this identifier to cite or link to this item: https://dspace.lboro.ac.uk/2134/37141

Title: Visualisation of electronic excited-state correlation in real space
Authors: Plasser, Felix
Keywords: Quantum chemistry
Excited states
Wavefunction analysis
Issue Date: 2019
Publisher: © Wiley
Citation: PLASSER, F., 2019. Visualisation of electronic excited-state correlation in real space. Chemphotochem, doi:10.1002/cptc.201900014.
Abstract: A method for the visualisation of excited‐state electron correlation is introduced and shown to address two notorious problems in excited‐ state electronic structure theory, the analysis of excitonic correlation and the distinction between covalent and ionic wavefunction character. The method operates by representing the excited state in terms of electron and hole quasiparticles, fixing the hole on a fragment of the system and observing the resulting conditional electron density in real space. The application of this approach to oligothiophene, an exemplary conjugated polymer, illuminates excitonic correlation effects of its excited states in unprecedented clarity and detail. A study of naphthalene shows that the distinction between the ionic and covalent states of this molecule, which has so far only been achieved using elaborate valence‐bond theory protocols, arises naturally in terms of electron‐hole avoidance and enhanced overlap, respectively. More generally, the method is relevant for any excited state that cannot be described by a single electronic configuration.
Description: This paper is closed access until 12 months after the date of publication.
Sponsor: Loughborough University
Version: Accepted for publication
DOI: 10.1002/cptc.201900014
URI: https://dspace.lboro.ac.uk/2134/37141
Publisher Link: https://doi.org/10.1002/cptc.201900014
ISSN: 2367-0932
Appears in Collections:Closed Access (Chemistry)

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