{"title":"A General and Transferable Local Hybrid Functional for Electronic Structure Theory and Many-Fermion Approaches.","authors":"Christof Holzer, Yannick J Franzke","doi":"10.1021/acs.jctc.4c01309","DOIUrl":null,"url":null,"abstract":"<p><p>Density functional theory has become the workhorse of quantum physics, chemistry, and materials science. Within these fields, a broad range of applications needs to be covered. These applications range from solids to molecular systems, from organic to inorganic chemistry, or even from electrons to other Fermions, such as protons or muons. This is emphasized by the plethora of density functional approximations that have been developed for various cases. In this work, two new local hybrid exchange-correlation density functionals are constructed from first-principles, promoting generality and transferability. We show that constraint satisfaction can be achieved even for admixtures with full exact exchange, without sacrificing accuracy. The performance of the new functionals CHYF-PBE and CHYF-B95 is assessed for thermochemical properties, excitation energies, Mössbauer isomer shifts, NMR spin-spin coupling constants, NMR shieldings and shifts, magnetizabilities, and EPR hyperfine coupling constants. Here, the new density functional shows excellent performance throughout all tests and is numerically robust only requiring small grids for converged results. Additionally, both functionals can easily be generalized to arbitrary Fermions as shown for electron-proton correlation energies. Therefore, we outline that density functionals generated in this way are general purpose tools for quantum mechanical studies.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":""},"PeriodicalIF":5.7000,"publicationDate":"2024-12-20","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.4c01309","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A General and Transferable Local Hybrid Functional for Electronic Structure Theory and Many-Fermion Approaches.
Density functional theory has become the workhorse of quantum physics, chemistry, and materials science. Within these fields, a broad range of applications needs to be covered. These applications range from solids to molecular systems, from organic to inorganic chemistry, or even from electrons to other Fermions, such as protons or muons. This is emphasized by the plethora of density functional approximations that have been developed for various cases. In this work, two new local hybrid exchange-correlation density functionals are constructed from first-principles, promoting generality and transferability. We show that constraint satisfaction can be achieved even for admixtures with full exact exchange, without sacrificing accuracy. The performance of the new functionals CHYF-PBE and CHYF-B95 is assessed for thermochemical properties, excitation energies, Mössbauer isomer shifts, NMR spin-spin coupling constants, NMR shieldings and shifts, magnetizabilities, and EPR hyperfine coupling constants. Here, the new density functional shows excellent performance throughout all tests and is numerically robust only requiring small grids for converged results. Additionally, both functionals can easily be generalized to arbitrary Fermions as shown for electron-proton correlation energies. Therefore, we outline that density functionals generated in this way are general purpose tools for quantum mechanical studies.
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.