Journal Article

FZJ-2017-07872

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Local Electron Correlation Treatment in Extended Multireference Calculations: Effect of Acceptor–Donor Substituents on the Biradical Character of the Polycyclic Aromatic Hydrocarbon Heptazethrene

Das, A. ; Mueller, T. (Corresponding author)FZJ* ; Plasser, F. ; Krisiloff, D. B. ; Carter, E. A. ; Lischka, H. (Corresponding author)

2017
Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.jctc.7b00156

Abstract: The implementation of a local correlation (LC) treatment of multireference (MR) configuration interaction approaches within the COLUMBUS program system is reported. The LC treatment is based on the weak pairs approximation of Sæbø and Pulay (Ann. Rev. Phys. Chem. 1993, 44, 213) and a geometrical analysis of Walter et al. (Chem. Phys. Lett. 2001, 346, 177). The removal of simultaneous single excitations out of the weak pairs is based on the reference doubly occupied space only, leading to a straightforward program implementation and a conceptual simplicity in terms of well-defined localized orbitals. Reductions of up to an order of magnitude in the configuration space expansion and in computer time for the Davidson diagonalization step are found. The selection of the active and the virtual orbital spaces is not affected by this procedure. This treatment is successfully applied to the singlet biradical heptazethrene and its different acceptor–donor substituents: 4,12-dicyanoheptazethrene, 4,12-diaminoheptazethrene, and 4-amino-12-cyanoheptazethrene. Simultaneous insertion of pairs of donor and acceptor groups increases the biradical character; for push–pull substitution, this effect is significantly smaller. In addition, results obtained from spin-corrected unrestricted density functional theory calculations are supported by our MR calculations.

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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 2017

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Database coverage:
; Current Contents - Physical, Chemical and Earth Sciences ; IF >= 5 ; JCR ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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