Electronic Properties of Cyclacenes from TAO-DFT

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...

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Main Authors:	Wu, Chun-Shian, Lee, Pei-Yin, Chai, Jeng-Da
Format:	Online
Language:	English
Published:	Nature Publishing Group 2016
Online Access:	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5112520/

id	pubmed-5112520
recordtype	oai_dc
spelling	pubmed-51125202016-11-23 Electronic Properties of Cyclacenes from TAO-DFT Wu, Chun-Shian Lee, Pei-Yin Chai, Jeng-Da Article 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. Nature Publishing Group 2016-11-17 /pmc/articles/PMC5112520/ /pubmed/27853249 http://dx.doi.org/10.1038/srep37249 Text en Copyright © 2016, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
repository_type	Open Access Journal
institution_category	Foreign Institution
institution	US National Center for Biotechnology Information
building	NCBI PubMed
collection	Online Access
language	English
format	Online
author	Wu, Chun-Shian Lee, Pei-Yin Chai, Jeng-Da
spellingShingle	Wu, Chun-Shian Lee, Pei-Yin Chai, Jeng-Da Electronic Properties of Cyclacenes from TAO-DFT
author_facet	Wu, Chun-Shian Lee, Pei-Yin Chai, Jeng-Da
author_sort	Wu, Chun-Shian
title	Electronic Properties of Cyclacenes from TAO-DFT
title_short	Electronic Properties of Cyclacenes from TAO-DFT
title_full	Electronic Properties of Cyclacenes from TAO-DFT
title_fullStr	Electronic Properties of Cyclacenes from TAO-DFT
title_full_unstemmed	Electronic Properties of Cyclacenes from TAO-DFT
title_sort	electronic properties of cyclacenes from tao-dft
description	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.
publisher	Nature Publishing Group
publishDate	2016
url	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5112520/
_version_	1613729887674171392

Electronic Properties of Cyclacenes from TAO-DFT

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