Electronic Properties of Cyclacenes from TAO-DFT

TL;DR

This paper employs the newly developed TAO-DFT method to accurately predict the electronic properties of cyclacenes with up to 100 fused benzene rings, revealing oscillatory behaviors and increasing polyradical character.

Contribution

The study introduces TAO-DFT for large cyclacenes, providing detailed insights into their electronic properties and the influence of cyclic topology, which were challenging for traditional methods.

Findings

Ground states of cyclacenes are singlets for all studied cases.

Electronic properties of cyclacenes oscillate with increasing ring number (n <= 30).

Larger cyclacenes show increased polyradical character at the periphery.

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.