Department of Physical Chemistry, University of Alicante, E-03080 Alicante, Spain.
ITODYS, CNRS, Université Paris Cité, F-75006 Paris, France.
J Chem Phys. 2023 Jan 28;158(4):044105. doi: 10.1063/5.0134946.
A family of non-empirical double-hybrid (DH) density functionals, such as Perdew-Burke-Ernzerhof (PBE)0-DH, PBE-QIDH, and their range-separated exchange (RSX) versions RSX-0DH and RSX-QIDH, all using Perdew-Burke-Ernzerhof(PBE) exchange and correlationfunctionals, is applied here to calculate the excitation energies for increasingly longer linear and cyclic acenes as part of their intense benchmarking for excited states of all types. The energies for the two lowest-lying singlet L and L states of linear oligoacenes as well as the triplet L and L states, are calculated and compared with experimental results. These functionals clearly outperform the results obtained from hybrid functionals and favorably compare with other double-hybrid expressions also tested here, such as B2-PLYP, B2GP-PLYP, ωB2-PLYP, and ωB2GP-PLYP. The study is complemented by the computation of adiabatic S-T singlet-triplet energy difference for linear acenes as well as the extension of the study to strained cyclic oligomers, showing how the family of non-empirical expressions robustly leads to competitive results.
我们应用非经验性双杂化（DH）密度泛函家族，如 Perdew-Burke-Ernzerhof（PBE）0-DH、PBE-QIDH 及其范围分离交换（RSX）版本 RSX-0DH 和 RSX-QIDH，它们都使用 Perdew-Burke-Ernzerhof（PBE）交换和相关泛函，来计算越来越长的线性和环状并五苯族的激发能，作为对各种激发态的激烈基准测试的一部分。计算并比较了线性寡聚并五苯族的两个最低的单线态 L 和 L 态以及三重态 L 和 L 态的能量与实验结果。这些泛函明显优于混合泛函的结果，并与这里也测试的其他双杂化表达式，如 B2-PLYP、B2GP-PLYP、ωB2-PLYP 和 ωB2GP-PLYP，进行了有利的比较。这项研究还包括线性并五苯族的绝热 S-T 单线态-三线态能量差的计算，以及对应变环状低聚物的研究扩展，展示了非经验性表达式家族如何稳健地得出有竞争力的结果。
