An MS-CASPT2 Calculation of the Excited Electronic States of an Axial Difluoroborondipyrromethene (BODIPY) Dimer,Journal of Chemical Theory and Computation

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An MS-CASPT2 Calculation of the Excited Electronic States of an Axial Difluoroborondipyrromethene (BODIPY) Dimer
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-06-06 00:00:00 , DOI: 10.1021/acs.jctc.8b00136
Jin Wen ₁ , Bowen Han ₂ , Zdeněk Havlas ₁ , Josef Michl _{1,

2}

Affiliation

The previously reported (Duman et al., J. Org. Chem. 2012, 77, 4516) calculated state energies of monomeric difluoroborondipyrromethene (BODIPY) and its axial dimer would suggest that these dyes are promising candidates for singlet fission, and the dimer was computed to have an unusual low-lying doubly excited state. We find that these results were affected by the use of an imbalanced active space in multireference calculations and are not correct. Multistate complete-active-space second-order perturbation theory (MS-CASPT2/cc-pVDZ) calculations using an [8,8] (8 electrons in 8 orbitals) active space for the monomer and a [16,16] active space for the dimer reproduce quite well the observed excitation energies of the S₁ states of both, and yield T₁ excitation energies well in excess of half of the S₁ excitation energies. We conclude that neither BODIPY monomer nor its axial dimer would permit exothermic singlet fission and are not worthy of investigation as potentially useful candidates, and that the unusual low-energy doubly excited states of the dimer were artifacts.

中文翻译：

轴向二氟硼联吡啶二甲亚甲基（BODIPY）二聚体的激发电子态的MS-CASPT2计算

以前的报道（杜曼等，J.Org。化学。2012，77，4516）计算的状态单体difluoroborondipyrromethene（BODIPY）及其轴向二聚体的能量会建议这些染料是有希望的单核裂变的候选人，以及二聚体计算有一个不寻常的低洼倍加兴奋状态。我们发现这些结果受到多参考计算中不平衡活动空间的使用的影响，并且是不正确的。多态完全有源空间二阶摄动理论（MS-CASPT2 / cc-pVDZ）计算使用单体的[8,8]（8个轨道中的8个电子）有效空间，以及[16,16]的有效空间二聚体很好地再现了观察到的两种状态下S _1的激发能，并产生T ₁激发能远远超过S ₁激发能的一半。我们得出的结论是，BODIPY单体及其轴向二聚体均不允许放热单线裂变，因此不值得作为潜在有用的候选物进行研究，并且二聚体的异常低能双激发态是伪像。

更新日期：2018-06-06

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