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.

arXiv commentaccepted for publication in Sci. Rep., 24 pages, 10 figures, supplementary material not included

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Cited by in corpus (10)

• Effect of Li Adsorption on the Electronic and Hydrogen Storage Properties of Acenes: A Dispersion-Corrected TAO-DFT Study
• Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes
• Fully numerical calculations on atoms with fractional occupations. Range-separated exchange functionals
• Polyacenes and diffuse interstellar bands
• Short- and long-range corrected hybrid density functionals with the D3 dispersion corrections
• Effect of Li Termination on the Electronic and Hydrogen Storage Properties of Linear Carbon Chains: A TAO-DFT Study
• Fate of the open-shell singlet ground state in the experimentally accessible acenes: a quantum Monte Carlo study
• Excitation Energies from Thermally-Assisted-Occupation Density Functional Theory: Theory and Computational Implementation
• Correlation between UV resilience and wavelength of narrow DIBs
• Finite-Temperature Thermally-Assisted-Occupation Density Functional Theory, Ab Initio Molecular Dynamics, and Quantum Mechanics/Molecular Mechanics Methods