Steffen Fauser, Viktoria Drontschenko, Christian Ochsenfeld, Andreas Görling
{"title":"使用 σ 函数的精确核磁共振屏蔽。","authors":"Steffen Fauser, Viktoria Drontschenko, Christian Ochsenfeld, Andreas Görling","doi":"10.1021/acs.jctc.4c00512","DOIUrl":null,"url":null,"abstract":"<p><p>In recent years, density-functional methods relying on a new type of fifth-rung correlation functionals called σ-functionals have been introduced. σ-Functionals are technically closely related to the random phase approximation and require the same computational effort but yield distinctively higher accuracies for reaction and transition state energies of main group chemistry and even outperform double-hybrid functionals for these energies. In this work, we systematically investigate how accurate σ-functionals can describe nuclear magnetic resonance (NMR) shieldings. It turns out that σ-functionals yield very accurate NMR shieldings, even though in their optimization, exclusively, energies are employed as reference data and response properties such as NMR shieldings are not involved at all. This shows that σ-functionals combine universal applicability with accuracy. Indeed, the NMR shieldings from a σ-functional using input orbitals and eigenvalues from Kohn-Sham calculations with the exchange-correlation functional of Perdew, Burke and Ernzerhof (PBE) turned out to be the most accurate ones among the NMR shieldings calculated with various density-functional methods including methods using double-hybrid functionals. That σ-functionals can be used for calculating both reliable energies and response properties like NMR shieldings characterizes them as all-purpose functionals, which is appealing from an application point of view.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":null,"pages":null},"PeriodicalIF":5.7000,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Accurate NMR Shieldings with σ-Functionals.\",\"authors\":\"Steffen Fauser, Viktoria Drontschenko, Christian Ochsenfeld, Andreas Görling\",\"doi\":\"10.1021/acs.jctc.4c00512\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>In recent years, density-functional methods relying on a new type of fifth-rung correlation functionals called σ-functionals have been introduced. σ-Functionals are technically closely related to the random phase approximation and require the same computational effort but yield distinctively higher accuracies for reaction and transition state energies of main group chemistry and even outperform double-hybrid functionals for these energies. In this work, we systematically investigate how accurate σ-functionals can describe nuclear magnetic resonance (NMR) shieldings. It turns out that σ-functionals yield very accurate NMR shieldings, even though in their optimization, exclusively, energies are employed as reference data and response properties such as NMR shieldings are not involved at all. This shows that σ-functionals combine universal applicability with accuracy. Indeed, the NMR shieldings from a σ-functional using input orbitals and eigenvalues from Kohn-Sham calculations with the exchange-correlation functional of Perdew, Burke and Ernzerhof (PBE) turned out to be the most accurate ones among the NMR shieldings calculated with various density-functional methods including methods using double-hybrid functionals. That σ-functionals can be used for calculating both reliable energies and response properties like NMR shieldings characterizes them as all-purpose functionals, which is appealing from an application point of view.</p>\",\"PeriodicalId\":45,\"journal\":{\"name\":\"Journal of Chemical Theory and Computation\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.7000,\"publicationDate\":\"2024-07-05\",\"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.4c00512\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.jctc.4c00512","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
In recent years, density-functional methods relying on a new type of fifth-rung correlation functionals called σ-functionals have been introduced. σ-Functionals are technically closely related to the random phase approximation and require the same computational effort but yield distinctively higher accuracies for reaction and transition state energies of main group chemistry and even outperform double-hybrid functionals for these energies. In this work, we systematically investigate how accurate σ-functionals can describe nuclear magnetic resonance (NMR) shieldings. It turns out that σ-functionals yield very accurate NMR shieldings, even though in their optimization, exclusively, energies are employed as reference data and response properties such as NMR shieldings are not involved at all. This shows that σ-functionals combine universal applicability with accuracy. Indeed, the NMR shieldings from a σ-functional using input orbitals and eigenvalues from Kohn-Sham calculations with the exchange-correlation functional of Perdew, Burke and Ernzerhof (PBE) turned out to be the most accurate ones among the NMR shieldings calculated with various density-functional methods including methods using double-hybrid functionals. That σ-functionals can be used for calculating both reliable energies and response properties like NMR shieldings characterizes them as all-purpose functionals, which is appealing from an application point of view.
期刊介绍:
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.