{"title":"模拟一系列共价连接的 TIPS 五烯中三重对状态的全自旋流形。","authors":"Timo Schulz, Christel M. Marian","doi":"10.1002/jcc.27475","DOIUrl":null,"url":null,"abstract":"<p>Combined density functional theory and multireference configuration interaction methods have been used to elucidate singlet fission (SF) pathways and mechanisms in three regioisomers of side-on linked pentacene dimers. In addition to the optically bright singlets (S<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msub>\n </mrow></math> and S<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>2</mn>\n </mrow>\n </msub>\n </mrow></math>) and singly excited triplets (T<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msub>\n </mrow></math> and T<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>2</mn>\n </mrow>\n </msub>\n </mrow></math>), the full spin manifold of multiexcitonic triplet-pair states (<span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msup>\n </mrow></math>ME, <span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>3</mn>\n </mrow>\n </msup>\n </mrow></math>ME, <span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>5</mn>\n </mrow>\n </msup>\n </mrow></math>ME) has been considered. In the <i>ortho</i>- and <i>para</i>-regioisomers, the <span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msup>\n </mrow></math>ME and S<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msub>\n </mrow></math> potentials intersect upon geometry relaxation of the S<span></span><math>\n <mrow>\n <msub>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msub>\n </mrow></math> excitation. In the <i>meta</i>-regioisomer, the crossing occurs upon delocalization of the optically bright excitation. The energetic accessibility of these conical intersections and the absence of low-lying charge-transfer states suggests a direct SF mechanism, assisted by charge-resonance effects in the <span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>1</mn>\n </mrow>\n </msup>\n </mrow></math>ME state. While the <span></span><math>\n <mrow>\n <msup>\n <mo> </mo>\n <mrow>\n <mn>5</mn>\n </mrow>\n </msup>\n </mrow></math>ME state does not appear to play a role in the SF mechanism of the <i>ortho</i>- and <i>para</i>-regioisomers, its participation in the disentanglement of the triplet pair is conceivable in the <i>meta</i>-regioisomer.</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"45 32","pages":"2727-2738"},"PeriodicalIF":3.4000,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.27475","citationCount":"0","resultStr":"{\"title\":\"Simulating the full spin manifold of triplet-pair states in a series of covalently linked TIPS-pentacenes\",\"authors\":\"Timo Schulz, Christel M. 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In addition to the optically bright singlets (S<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msub>\\n </mrow></math> and S<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>2</mn>\\n </mrow>\\n </msub>\\n </mrow></math>) and singly excited triplets (T<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msub>\\n </mrow></math> and T<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>2</mn>\\n </mrow>\\n </msub>\\n </mrow></math>), the full spin manifold of multiexcitonic triplet-pair states (<span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME, <span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>3</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME, <span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>5</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME) has been considered. In the <i>ortho</i>- and <i>para</i>-regioisomers, the <span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME and S<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msub>\\n </mrow></math> potentials intersect upon geometry relaxation of the S<span></span><math>\\n <mrow>\\n <msub>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msub>\\n </mrow></math> excitation. In the <i>meta</i>-regioisomer, the crossing occurs upon delocalization of the optically bright excitation. The energetic accessibility of these conical intersections and the absence of low-lying charge-transfer states suggests a direct SF mechanism, assisted by charge-resonance effects in the <span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>1</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME state. While the <span></span><math>\\n <mrow>\\n <msup>\\n <mo> </mo>\\n <mrow>\\n <mn>5</mn>\\n </mrow>\\n </msup>\\n </mrow></math>ME state does not appear to play a role in the SF mechanism of the <i>ortho</i>- and <i>para</i>-regioisomers, its participation in the disentanglement of the triplet pair is conceivable in the <i>meta</i>-regioisomer.</p>\",\"PeriodicalId\":188,\"journal\":{\"name\":\"Journal of Computational Chemistry\",\"volume\":\"45 32\",\"pages\":\"2727-2738\"},\"PeriodicalIF\":3.4000,\"publicationDate\":\"2024-08-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.27475\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Computational Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/jcc.27475\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Computational Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jcc.27475","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
研究人员采用密度泛函理论和多参量构型相互作用相结合的方法,阐明了侧向连接的并五苯二聚体的三种区域异构体中单子裂变(SF)的途径和机制。除了光学上明亮的单子(S 1 $$ {}_1 $$ 和 S 2 $$ {}_2 $$)和单激发的三子(T 1 $$ {}_1 $$ 和 T 2 $$ {}_2 $$)之外,我们还考虑了多激发三子对状态(1 $$ {}^1 $$ ME、3 $$ {}^3 $$ ME、5 $$ {}^5 $$ ME)的全自旋流形。在正偏异构体和准偏异构体中,1 $$ {}^1 $$ ME 和 S 1 $$ {}_1 $$ 电位在 S 1 $$ {}_1 $ 激发的几何弛豫时相交。在元孤岛异构体中,交叉发生在光亮激发的分散过程中。这些锥形交叉的能量可及性和低洼电荷转移态的缺失表明,在 1 $$ {}^1 $ ME 状态的电荷共振效应的辅助下,存在一种直接的 SF 机制。虽然 5 $$ {}^5 $ ME 状态在正对和对位孤岛异构体的 SF 机制中似乎不起作用,但在元孤岛异构体中,它参与三重对的解缠是可以想象的。
Simulating the full spin manifold of triplet-pair states in a series of covalently linked TIPS-pentacenes
Combined density functional theory and multireference configuration interaction methods have been used to elucidate singlet fission (SF) pathways and mechanisms in three regioisomers of side-on linked pentacene dimers. In addition to the optically bright singlets (S and S) and singly excited triplets (T and T), the full spin manifold of multiexcitonic triplet-pair states (ME, ME, ME) has been considered. In the ortho- and para-regioisomers, the ME and S potentials intersect upon geometry relaxation of the S excitation. In the meta-regioisomer, the crossing occurs upon delocalization of the optically bright excitation. The energetic accessibility of these conical intersections and the absence of low-lying charge-transfer states suggests a direct SF mechanism, assisted by charge-resonance effects in the ME state. While the ME state does not appear to play a role in the SF mechanism of the ortho- and para-regioisomers, its participation in the disentanglement of the triplet pair is conceivable in the meta-regioisomer.
期刊介绍:
This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.