Jiyoon Choi, Kyungtae Kang, Ji Hun Park, Hyungjun Kim
{"title":"基于密度泛函理论的吖啶衍生物基态和激发态还原电位的快速准确估算","authors":"Jiyoon Choi, Kyungtae Kang, Ji Hun Park, Hyungjun Kim","doi":"10.1002/poc.4641","DOIUrl":null,"url":null,"abstract":"<p>We devised a quantum chemical simulation protocol that can rapidly and accurately predict ground and excited state reduction potentials (<i>E</i><sup>0</sup> and <i>E</i>*, respectively) of acridinium photoredox catalysts (PCs). To bypass time-consuming excited state geometry optimizations, we used ground state equilibrium geometries to compute the electronic energy of excited states, which provides reasonable <i>E</i><sup>0</sup> and <i>E</i>* estimates. The contribution of Hartree-Fock exchange (HFX) in density functionals was systematically varied to estimate <i>E</i><sup>0</sup> and <i>E</i>*. In addition to reproducing experimental results, physically sensible models, such as correct descriptions of exciton behavior, are highly necessary. Based on the exciton correlation values, the appropriate amount of HFX in the B3LYP functional was determined to be 30 % to yield physically sensible bound electron-hole pairs for small organic molecules. We also investigated the impact of basis sets on the predictability of <i>E</i><sup>0</sup> and <i>E</i>*. Geometry optimizations with B3LYP-D2(HFX 20 %)/6-31G and single point energy refinement with (TD-)B3LYP-D2(HFX 30%)/6-311++G(d,p) yielded the best results. The transferability of the suggested protocol was confirmed with a test set consisting of eight acridinium derivatives. This study can provide reasonably accurate results with relatively small amounts of computational resources, and it is therefore expected to greatly contribute to the development of new acridinium PCs.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Density functional theory-based rapid and accurate estimation of reduction potentials of acridinium derivatives in ground and excited state\",\"authors\":\"Jiyoon Choi, Kyungtae Kang, Ji Hun Park, Hyungjun Kim\",\"doi\":\"10.1002/poc.4641\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>We devised a quantum chemical simulation protocol that can rapidly and accurately predict ground and excited state reduction potentials (<i>E</i><sup>0</sup> and <i>E</i>*, respectively) of acridinium photoredox catalysts (PCs). To bypass time-consuming excited state geometry optimizations, we used ground state equilibrium geometries to compute the electronic energy of excited states, which provides reasonable <i>E</i><sup>0</sup> and <i>E</i>* estimates. The contribution of Hartree-Fock exchange (HFX) in density functionals was systematically varied to estimate <i>E</i><sup>0</sup> and <i>E</i>*. In addition to reproducing experimental results, physically sensible models, such as correct descriptions of exciton behavior, are highly necessary. Based on the exciton correlation values, the appropriate amount of HFX in the B3LYP functional was determined to be 30 % to yield physically sensible bound electron-hole pairs for small organic molecules. We also investigated the impact of basis sets on the predictability of <i>E</i><sup>0</sup> and <i>E</i>*. Geometry optimizations with B3LYP-D2(HFX 20 %)/6-31G and single point energy refinement with (TD-)B3LYP-D2(HFX 30%)/6-311++G(d,p) yielded the best results. The transferability of the suggested protocol was confirmed with a test set consisting of eight acridinium derivatives. This study can provide reasonably accurate results with relatively small amounts of computational resources, and it is therefore expected to greatly contribute to the development of new acridinium PCs.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2024-06-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4641\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4641","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Density functional theory-based rapid and accurate estimation of reduction potentials of acridinium derivatives in ground and excited state
We devised a quantum chemical simulation protocol that can rapidly and accurately predict ground and excited state reduction potentials (E0 and E*, respectively) of acridinium photoredox catalysts (PCs). To bypass time-consuming excited state geometry optimizations, we used ground state equilibrium geometries to compute the electronic energy of excited states, which provides reasonable E0 and E* estimates. The contribution of Hartree-Fock exchange (HFX) in density functionals was systematically varied to estimate E0 and E*. In addition to reproducing experimental results, physically sensible models, such as correct descriptions of exciton behavior, are highly necessary. Based on the exciton correlation values, the appropriate amount of HFX in the B3LYP functional was determined to be 30 % to yield physically sensible bound electron-hole pairs for small organic molecules. We also investigated the impact of basis sets on the predictability of E0 and E*. Geometry optimizations with B3LYP-D2(HFX 20 %)/6-31G and single point energy refinement with (TD-)B3LYP-D2(HFX 30%)/6-311++G(d,p) yielded the best results. The transferability of the suggested protocol was confirmed with a test set consisting of eight acridinium derivatives. This study can provide reasonably accurate results with relatively small amounts of computational resources, and it is therefore expected to greatly contribute to the development of new acridinium PCs.
期刊介绍:
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.