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We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to shortcomings in the underlying linear response method, with final results from less accurate starting points nearly as good as those from the best starting points. This pattern is especially stark in charge transfer states, where the approach converts starting points with multi-eV errors into post-linear-response results with errors on the order of 0.1 eV. These findings highlight the ability of Aufbau suppressed coupled cluster to perform its own orbital relaxations and raise the question of whether initializing it with an orbital relaxed reference is worth the trouble.
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http://dx.doi.org/10.1021/acs.jctc.5c01027 | DOI Listing |
J Chem Theory Comput
September 2025
Department of Chemistry, University of California, Berkeley, California 94720, United States.
We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to shortcomings in the underlying linear response method, with final results from less accurate starting points nearly as good as those from the best starting points. This pattern is especially stark in charge transfer states, where the approach converts starting points with multi-eV errors into post-linear-response results with errors on the order of 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Marine Functional Polymers Research Center (MFPRC), School of Materials Science and Engineering, Hainan University, No 58, Renmin Avenue, Haikou, 570228, China.
High-performance luminescent radicals featuring donor-radical (D-R) charge-transfer (CT) excited states have emerged as promising candidates for optoelectronic applications. However, prior studies have predominantly focused on through-bond charge-transfer (TBCT) mechanisms. In this work, we report the first examples of luminescent radicals based on TTM (tris(2,4,6-trichlorophenyl)methyl radical) with through-space charge-transfer (TSCT) excited states, represented by TPA-FR-TTM and CZP-FR-TTM.
View Article and Find Full Text PDFJ Phys Chem Lett
August 2025
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Modeling charge transfer well can require treating postexcitation orbital relaxations and handling medium to large molecules in realistic environments. By combining a state-specific correlation treatment with such orbital relaxations, Aufbau suppressed coupled cluster has proven to be accurate for charge transfer, but like many coupled cluster methods, it struggles with large system sizes. We derive a low-cost Aufbau suppressed second-order perturbation theory and show that by nesting a small coupled cluster treatment inside of it, computational cost and scaling are reduced while accuracy is maintained.
View Article and Find Full Text PDFJ Chem Theory Comput
April 2025
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Guided by perturbative analysis, we improve the accuracy of Aufbau suppressed coupled cluster theory in simple single excitations, multiconfigurational single excitations, and charge transfer excitations while keeping the cost of its leading-order terms precisely in line with ground-state coupled cluster. Combining these accuracy improvements with a more efficient implementation based on spin adaptation, we observe high accuracy in a large test set of single excitations and, in particular, a mean unsigned error for charge transfer states that outperforms equation-of-motion coupled cluster theory by 0.25 eV.
View Article and Find Full Text PDFMolecules
March 2025
College of Chemistry and Chemical Engineering, Xinjiang Agricultural University, East Road No. 311, Urumqi 830052, China.
In this study, we report two novel donor-acceptor (D-A•)-type triphenylmethyl radicals, TTM-1TPE-2Cz and TTM-2TPE-2Cz, synthesized by integrating an aggregation-induced emission (AIE)-active 2-(1, 2, 2-triphenylethenyl)-9H-carbazole (TPE-2Cz) donor with tris(2,4,6-trichlorophenyl)methyl (TTM) radical core. Despite the AIE unit's conventional ACQ-suppressing capability, both radicals exhibit complete emission quenching in solid/solution states but demonstrate 655 nm red emission in polymethyl methacrylate (PMMA)-doped films. Theoretical and experimental analyses reveal that the flexible TPE moiety unexpectedly enhances non-radiative decay while establishing a non-Aufbau electronic configuration through its strong electron-donating nature (-5.
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