Advances in quantum chemistry最新文献

筛选

英文中文

Multistate density functional theory for local and charge-transfer tripdoublet states from triplet-free radical interactions. 三重自由基相互作用中局部态和电荷转移三重态的多态密度泛函理论。

Advances in quantum chemistry Pub Date : 2025-01-01 Epub Date: 2025-06-24 DOI: 10.1016/bs.aiq.2025.03.010

Chenyu Liu, Yang Xu, Peng Bao, Yangyi Lu, Jiali Gao

{"title":"Multistate density functional theory for local and charge-transfer tripdoublet states from triplet-free radical interactions.","authors":"Chenyu Liu, Yang Xu, Peng Bao, Yangyi Lu, Jiali Gao","doi":"10.1016/bs.aiq.2025.03.010","DOIUrl":"10.1016/bs.aiq.2025.03.010","url":null,"abstract":"<p><p>The interaction between excited states of a closed-shell chromophore and a nearby free radical species gives rise to spin-coupled doublet states, namely singdoublet and tripdoublet, as well as a quartet state. This coupling facilitates transitions that are otherwise spin-forbidden, thereby enhancing intersystem crossing and influencing luminescence and non-radiative decay pathways. In this chapter, we explore these interactions using multistate density functional theory (MSDFT). By employing a minimal active space (MAS) comprising just ten determinant configurations, MSDFT effectively captures local and charge-transfer excitations with inclusion of correlation effects. MSDFT extends the Hohenberg-Kohn density functional theory from the ground state to encompass all electronic states, underscoring the potential for developing computationally efficient methods to study excited states. Numerical results demonstrate that MSDFT accurately reproduces both qualitative trends and quantitative excited-state energies, in accord with previous studies using extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2). The work explores energy changes along a reaction path from the <math> <msub><mrow><mi>D</mi></mrow> <mrow><mn>0</mn></mrow> </msub> <mo>/</mo> <msub><mrow><mi>D</mi></mrow> <mrow><mn>1</mn></mrow> </msub> </math> minimum energy crossing intersection to the <math> <msub><mrow><mi>D</mi></mrow> <mrow><mn>2</mn></mrow> </msub> <mo>/</mo> <msub><mrow><mi>D</mi></mrow> <mrow><mn>3</mn></mrow> </msub> </math> crossing in the exciplex formed by 10-methylphenothiazine and a dicarboximide electron acceptor linked to the stable free radical 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO).</p>","PeriodicalId":521154,"journal":{"name":"Advances in quantum chemistry","volume":"91 ","pages":"223-250"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12717433/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0