TY  - JOUR
AU  - Horn, Shawn
AU  - Plasser, Felix
AU  - Mueller, Thomas
AU  - Libisch, Florian
AU  - Burgdörfer, Joachim
AU  - Lischka, Hans
TI  - A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory
JO  - Theoretical chemistry accounts
VL  - 133
IS  - 8
SN  - 1432-2234
CY  - Berlin
PB  - Springer
M1  - FZJ-2014-05994
SP  - 1511
PY  - 2014
AB  - This study examines the radical nature and spin symmetry of the ground state of the quasi-linear acene and two-dimensional periacene series. For this purpose, high-level ab initio calculations have been performed using the multireference averaged quadratic coupled cluster theory and the COLUMBUS program package. A reference space consisting of restricted and complete active spaces is taken for the pi-conjugated space, correlating 16 electrons with 16 orbitals with the most pronounced open-shell character for the acenes and a complete active-space reference approach with eight electrons in eight orbitals for the periacenes. This reference space is used to construct the total configuration space by means of single and double excitations. By comparison with more extended calculations, it is shown that a focus on the pi space with a 6-31G basis set is sufficient to describe the major features of the electronic character of these compounds. The present findings suggest that the ground state is a singlet for the smaller members of these series, but that for the larger ones, singlet and triplet states are quasi-degenerate. Both the acenes and periacenes exhibit significant polyradical character beyond the traditional diradical.
LB  - PUB:(DE-HGF)16
UR  - <Go to ISI:>//WOS:000337640400001
DO  - DOI:10.1007/s00214-014-1511-8
UR  - https://juser.fz-juelich.de/record/172529
ER  -