Correlation vs. exchange competition drives the singlet-triplet excited-state inversion in non-alternant hydrocarbons
Correlation vs. exchange competition drives the singlet-triplet excited-state inversion in non-alternant hydrocarbons
复制标题
相关与交换竞争驱动非交替碳氢化合物中的单重态-三重态激发态反转
DOI：
10.1039/d3cp02465b
复制
发表时间：
2023
影响因子：
3.3
通讯作者：
Sandoval-Salinas M
中科院分区：
文献类型：
--
作者：
Sandoval-Salinas M
在这项工作中，我们重点了解两种非苯型非交替碳氢化合物的S1-T1激发态能量反转背后的驱动力（这因此违反了洪德规则，使S1态的能量低于T1态），由奇元环组成。这里考虑的分子具有相同的化学组成，但在空间中具有不同的原子构型。微妙的结构和电子因素之间的相互作用，可能会引起反转和它的能量扩展，只有几毫电子伏，在这里系统地研究了国家的最先进的计算。定性和定量的准确预测，获得采用后HF方法，由于平衡和仔细列入电子相关效应。所获得的结果可能会指导和合理化新的搜索违反洪德规则的分子，伴随着展示的重要性，从理论方法的选择的关键贡献。
In this work, we focus on the understanding of the driving force behind the S1–T1 excited-state energy inversion (which would thus violate Hund's rule, making the S1 state lower in energy than the T1 state) of two non-benzenoid non-alternant hydrocarbons, composed of odd-membered rings. The molecules considered here have identical chemical composition but different atomic configuration in space. The delicate interplay between structural and electronic factors that might induce inversion and its energy extension, only by a few meV, is systematically investigated here by state-of-the-art calculations. Qualitative and quantitative accurate predictions are obtained employing post-HF methods, thanks to the balanced and careful inclusion of electron correlation effects. The obtained results might guide and rationalize new searches for molecules violating Hund's rule, concomitantly demonstrating the importance of key contributions from the theoretical method of choice.