title: Electronic Properties of Cyclacenes from TAO-DFT.
abstract: Owing to the presence of strong static correlation effects, accurate prediction of the electronic properties (e.g., the singlet-triplet energy gaps, vertical ionization potentials, vertical electron affinities, fundamental gaps, symmetrized von Neumann entropy, active orbital occupation numbers, and real-space representation of active orbitals) of cyclacenes with n fused benzene rings (n = 4-100) has posed a great challenge to traditional electronic structure methods. To meet the challenge, we study these properties using our newly developed thermally-assisted-occupation density functional theory (TAO-DFT), a very efficient method for the study of large systems with strong static correlation effects. Besides, to examine the role of cyclic topology, the electronic properties of cyclacenes are also compared with those of acenes. Similar to acenes, the ground states of cyclacenes are singlets for all the cases studied. In contrast to acenes, the electronic properties of cyclacenes, however, exhibit oscillatory behavior (for n ≤ 30) in the approach to the corresponding properties of acenes with increasing number of benzene rings. On the basis of the calculated orbitals and their occupation numbers, the larger cyclacenes are shown to exhibit increasing polyradical character in their ground states, with the active orbitals being mainly localized at the peripheral carbon atoms.
authors.affiliation: Department of Physics, National Taiwan University, Taipei 10617, Taiwan.|Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Chun-Shian
authors.initials: CS
authors.lastname: Wu
authors.affiliation: Department of Physics, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Pei-Yin
authors.initials: PY
authors.lastname: Lee
authors.affiliation: Department of Physics, National Taiwan University, Taipei 10617, Taiwan.|Center for Theoretical Sciences and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Jeng-Da
authors.initials: JD
authors.lastname: Chai