Electronic Properties of Ladder-Type Phenylenes Studied by Thermally-Assisted-Occupation Density Functional Theory
Abstract
Accurate prediction of the electronic properties of extended π-conjugated systems with radical character remains a major theoretical challenge. To overcome this challenge, thermally-assisted-occupation density functional theory (TAO-DFT) has been developed in recent years. In this study, we employ TAO-DFT to systematically explore the electronic properties of ladder-type phenylenes (n-LPs), containing n linearly fused four-membered carbon rings. Our calculations reveal that all investigated n-LPs (with n = 1 ~ 40) possess singlet ground states. With increasing n-LP length, we observe a transition from the nonradical character of shorter n-LPs to the polyradical character of longer n-LPs. Notably, we identify a distinct damped periodic oscillation in the radical character of n-LPs, featuring highly correlated hotspots at specific lengths (n = 3k − 1, where k are positive integers). The real-space representation of active orbitals confirms this global electronic behavior is governed by the intrinsic structural periodicity and completely delocalized nature of the active orbitals along the central ladder framework. These findings provide fundamental insights into the size-dependent electronic properties of n-LPs, guiding their rational design for future nanomaterial applications.
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BibTeX
@misc{wang2026electronic,
title = {{Electronic Properties of Ladder-Type Phenylenes Studied by Thermally-Assisted-Occupation Density Functional Theory}},
author = {Tsu-Hsuan Wang and Jeng-Da Chai},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.09783},
eprint = {2610.09783},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.09783},
}
RIS
TY - UNPB
TI - Electronic Properties of Ladder-Type Phenylenes Studied by Thermally-Assisted-Occupation Density Functional Theory
AU - Tsu-Hsuan Wang
AU - Jeng-Da Chai
PY - 2026
DA - 2026/10/15
PB - arXiv
DO - 10.48550/arxiv.2610.09783
UR - https://arxiv.org/abs/2610.09783
AB - Accurate prediction of the electronic properties of extended π-conjugated systems with radical character remains a major theoretical challenge. To overcome this challenge, thermally-assisted-occupation density functional theory (TAO-DFT) has been developed in recent years. In this study, we employ TAO-DFT to systematically explore the electronic properties of ladder-type phenylenes (n-LPs), containing n linearly fused four-membered carbon rings. Our calculations reveal that all investigated n-LPs (with n = 1 ~ 40) possess singlet ground states. With increasing n-LP length, we observe a transition from the nonradical character of shorter n-LPs to the polyradical character of longer n-LPs. Notably, we identify a distinct damped periodic oscillation in the radical character of n-LPs, featuring highly correlated hotspots at specific lengths (n = 3k − 1, where k are positive integers). The real-space representation of active orbitals confirms this global electronic behavior is governed by the intrinsic structural periodicity and completely delocalized nature of the active orbitals along the central ladder framework. These findings provide fundamental insights into the size-dependent electronic properties of n-LPs, guiding their rational design for future nanomaterial applications.
ER -