{"title":"运动方程正则化轨道优化二阶扰动理论与密度拟合近似。","authors":"Aslı Ünal, Uğur Bozkaya","doi":"10.1063/5.0223132","DOIUrl":null,"url":null,"abstract":"<p><p>The density-fitted equation-of-motion (EOM) orbital-optimized second-order perturbation theory (DF-EOM-OMP2) method is presented for the first time. In addition, κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods are implemented with the addition of κ-regularization. The accuracy of the DF-EOM-OMP2, κ-DF-EOM-MP2, and κ-DF-EOM-OMP2 methods are compared to the density-fitted EOM-MP2 (DF-EOM-MP2), EOM coupled-cluster (CC) singles and doubles (DF-EOM-CCSD), and EOM-CCSD with the triples excitation correction model [EOM-CCSD(fT)] for excitation energies of many closed- and open-shell chemical systems. The excitation energies computed using different test cases and methods were compared to the EOM-CCSD(fT) method and mean absolute errors (MAEs) are presented. The MAE values of closed- and open-shell cases (closed-shell organic chromophores set, open-shell set, peptide radicals set, and radical set) according to the EOM-CCSD(fT) method show that the κ-regularization technique yields highly accurate results for the first excited states. Our results indicate that the κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods perform noticeably better than the DF-EOM-MP2 and DF-EOM-OMP2 methods. They approach the EOM-CCSD quality, at a significantly reduced cost, for the computation of excitation energies. Especially, the κ-DF-EOM-MP2 method provides outstanding results for most test cases considered. Overall, we conclude that the κ-versions of DF-EOM-MP2 and DF-EOM-OMP2 emerge as a useful computational tool for the study of excited-state molecular properties.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Equation-of-motion regularized orbital-optimized second-order perturbation theory with the density-fitting approximation.\",\"authors\":\"Aslı Ünal, Uğur Bozkaya\",\"doi\":\"10.1063/5.0223132\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The density-fitted equation-of-motion (EOM) orbital-optimized second-order perturbation theory (DF-EOM-OMP2) method is presented for the first time. In addition, κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods are implemented with the addition of κ-regularization. The accuracy of the DF-EOM-OMP2, κ-DF-EOM-MP2, and κ-DF-EOM-OMP2 methods are compared to the density-fitted EOM-MP2 (DF-EOM-MP2), EOM coupled-cluster (CC) singles and doubles (DF-EOM-CCSD), and EOM-CCSD with the triples excitation correction model [EOM-CCSD(fT)] for excitation energies of many closed- and open-shell chemical systems. The excitation energies computed using different test cases and methods were compared to the EOM-CCSD(fT) method and mean absolute errors (MAEs) are presented. The MAE values of closed- and open-shell cases (closed-shell organic chromophores set, open-shell set, peptide radicals set, and radical set) according to the EOM-CCSD(fT) method show that the κ-regularization technique yields highly accurate results for the first excited states. Our results indicate that the κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods perform noticeably better than the DF-EOM-MP2 and DF-EOM-OMP2 methods. They approach the EOM-CCSD quality, at a significantly reduced cost, for the computation of excitation energies. Especially, the κ-DF-EOM-MP2 method provides outstanding results for most test cases considered. Overall, we conclude that the κ-versions of DF-EOM-MP2 and DF-EOM-OMP2 emerge as a useful computational tool for the study of excited-state molecular properties.</p>\",\"PeriodicalId\":15313,\"journal\":{\"name\":\"Journal of Chemical Physics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1063/5.0223132\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1063/5.0223132","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Equation-of-motion regularized orbital-optimized second-order perturbation theory with the density-fitting approximation.
The density-fitted equation-of-motion (EOM) orbital-optimized second-order perturbation theory (DF-EOM-OMP2) method is presented for the first time. In addition, κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods are implemented with the addition of κ-regularization. The accuracy of the DF-EOM-OMP2, κ-DF-EOM-MP2, and κ-DF-EOM-OMP2 methods are compared to the density-fitted EOM-MP2 (DF-EOM-MP2), EOM coupled-cluster (CC) singles and doubles (DF-EOM-CCSD), and EOM-CCSD with the triples excitation correction model [EOM-CCSD(fT)] for excitation energies of many closed- and open-shell chemical systems. The excitation energies computed using different test cases and methods were compared to the EOM-CCSD(fT) method and mean absolute errors (MAEs) are presented. The MAE values of closed- and open-shell cases (closed-shell organic chromophores set, open-shell set, peptide radicals set, and radical set) according to the EOM-CCSD(fT) method show that the κ-regularization technique yields highly accurate results for the first excited states. Our results indicate that the κ-DF-EOM-MP2 and κ-DF-EOM-OMP2 methods perform noticeably better than the DF-EOM-MP2 and DF-EOM-OMP2 methods. They approach the EOM-CCSD quality, at a significantly reduced cost, for the computation of excitation energies. Especially, the κ-DF-EOM-MP2 method provides outstanding results for most test cases considered. Overall, we conclude that the κ-versions of DF-EOM-MP2 and DF-EOM-OMP2 emerge as a useful computational tool for the study of excited-state molecular properties.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
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