Journal Article

FZJ-2016-03710

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Polyradical Character of Triangular Non-Kekulé Structures, Zethrenes, p -Quinodimethane-Linked Bisphenalenyl, and the Clar Goblet in Comparison: An Extended Multireference Study

Das, A. ; Mueller, T.FZJ* ; Plasser, F. ; Lischka, H. (Corresponding author)

2016
Soc. Washington, DC

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Please use a persistent id in citations: http://hdl.handle.net/2128/11773  doi:10.1021/acs.jpca.5b12393

Abstract: In this work, two different classes of polyaromatic hydrocarbon (PAH) systems have been investigated in order to characterize the amount of polyradical character and to localize the specific regions of chemical reactivity: (a) the non-Kekulé triangular structures phenalenyl, triangulene and a π-extended triangulene system with high-spin ground state and (b) PAHs based on zethrenes, p-quinodimethane-linked bisphenalenyl, and the Clar goblet containing varying polyradical character in their singlet ground state. The first class of structures already have open-shell character because of their high-spin ground state, which follows from the bonding pattern, whereas for the second class the open-shell character is generated either because of the competition between the closed-shell quinoid Kekulé and the open-shell singlet biradical resonance structures or the topology of the π-electron arrangement of the non-Kekulé form. High-level ab initio calculations based on multireference theory have been carried out to compute singlet–triplet splitting for the above-listed compounds and to provide insight into their chemical reactivity based on the polyradical character by means of unpaired densities. Unrestricted density functional theory and Hartree–Fock calculations have been performed for comparison also in order to obtain better insight into their applicability to these types of complicated radical systems.

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Contributing Institute(s):

1. Jülich Supercomputing Center (JSC)

Research Program(s):

1. 511 - Computational Science and Mathematical Methods (POF3-511) (POF3-511)

Appears in the scientific report 2016

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Database coverage:
; ; Current Contents - Physical, Chemical and Earth Sciences ; Free to read ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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