{"title":"Knowles Partitioning from a Stationary Condition: Single- and Multireference Case.","authors":"Ágnes Szabados, András Gombás, Péter R Surján","doi":"10.1021/acs.jctc.5c01147","DOIUrl":null,"url":null,"abstract":"<p><p>A stationary condition involving the first-order wave function of many-body perturbation theory (PT) is shown to lead to the partitioning introduced recently by Knowles (<i>J</i>. <i>Chem</i>. <i>Phys</i>., <i>156</i>, 011101 (<b>2022</b>)). This facilitates direct generalization for multireference (MR) PT schemes operating with a one-body Hamiltonian at zero-order. The essence of the method is an optimization of one-body integrals in the first-order interacting subspace, thereby achieving superior performance over Møller-Plesset (MP) type approaches. The stationary condition based extension, performed in the pivot-independent variant of the multiconfiguration PT (frame MCPT, fMCPT), rectifies the shortcomings of our previous MR adaptation. The resulting PT series comes close to the stationary condition-based extension, carried out in the complete active space PT (CASPT) formalism. Numerical results demonstrate that Knowles partitioning consistently outperforms MP partitioning in fMCPT.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":""},"PeriodicalIF":5.5000,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.jctc.5c01147","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
A stationary condition involving the first-order wave function of many-body perturbation theory (PT) is shown to lead to the partitioning introduced recently by Knowles (J. Chem. Phys., 156, 011101 (2022)). This facilitates direct generalization for multireference (MR) PT schemes operating with a one-body Hamiltonian at zero-order. The essence of the method is an optimization of one-body integrals in the first-order interacting subspace, thereby achieving superior performance over Møller-Plesset (MP) type approaches. The stationary condition based extension, performed in the pivot-independent variant of the multiconfiguration PT (frame MCPT, fMCPT), rectifies the shortcomings of our previous MR adaptation. The resulting PT series comes close to the stationary condition-based extension, carried out in the complete active space PT (CASPT) formalism. Numerical results demonstrate that Knowles partitioning consistently outperforms MP partitioning in fMCPT.
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The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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