TY  - JOUR
AU  - Das, Anita
AU  - Mueller, Thomas
AU  - Plasser, Felix
AU  - Krisiloff, David B.
AU  - Carter, Emily A.
AU  - Lischka, Hans
TI  - Local Electron Correlation Treatment in Extended Multireference Calculations: Effect of Acceptor–Donor Substituents on the Biradical Character of the Polycyclic Aromatic Hydrocarbon Heptazethrene
JO  - Journal of chemical theory and computation
VL  - 13
IS  - 6
SN  - 1549-9626
CY  - Washington, DC
M1  - FZJ-2017-07872
SP  - 2612 - 2622
PY  - 2017
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - pmid:28441477
UR  - <Go to ISI:>//WOS:000403530100023
DO  - DOI:10.1021/acs.jctc.7b00156
UR  - https://juser.fz-juelich.de/record/840330
ER  -