A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory

作者：Horn Shawn; Plasser Felix; Mueller Thomas; Libisch Florian; Burgdoerfer Joachim; Lischka Hans^*

来源：Theoretical Chemistry Accounts, 2014, 133(8): 1-9.

DOI：10.1007/s00214-014-1511-8

• Singlet-triplet splitting
• MR-AQCC
• Unpaired electron density
• Natural orbitals

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.

• 出版日期2014-6-15