Teagan Shane Costain, Jibrael B Rolston, Simon P Neville, Michael S Schuurman
{"title":"仅使用 ab initio 数据参数化的 DFT/MRCI 哈密顿参数。II.核心激发态。","authors":"Teagan Shane Costain, Jibrael B Rolston, Simon P Neville, Michael S Schuurman","doi":"10.1063/5.0227385","DOIUrl":null,"url":null,"abstract":"<p><p>A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J. Chem. Phys, 160, 224106 (2024)] is parameterized by fitting to benchmark quality ab initio data. The definition of the CVS-QE12 and QE8 Hamiltonians differ from previous CVS-DFT/MRCI parameterizations in three primary ways: (i) the replacement of the BHLYP exchange-correlation functional with QTP17 to yield a balanced description of both core and valence excitation energies, (ii) the adoption of a new, three-parameter damping function, and (iii) the introduction of separate scaling of the core-valence and valence-valence Coulombic interactions. Crucially, the parameters of the CVS-QE12 Hamiltonian are obtained via fitting exclusively to highly accurate ab initio vertical core-excitation and ionization energies computed at the CVS-EOM-CCSDT level of theory. The CVS-QE12 Hamiltonian is validated against further benchmark computations and is found to furnish K-edge core vertical excitation and ionization energies exhibiting absolute errors ≤0.5 eV at low computational cost.</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\":\"A DFT/MRCI Hamiltonian parameterized using only ab initio data. II. Core-excited states.\",\"authors\":\"Teagan Shane Costain, Jibrael B Rolston, Simon P Neville, Michael S Schuurman\",\"doi\":\"10.1063/5.0227385\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J. Chem. Phys, 160, 224106 (2024)] is parameterized by fitting to benchmark quality ab initio data. The definition of the CVS-QE12 and QE8 Hamiltonians differ from previous CVS-DFT/MRCI parameterizations in three primary ways: (i) the replacement of the BHLYP exchange-correlation functional with QTP17 to yield a balanced description of both core and valence excitation energies, (ii) the adoption of a new, three-parameter damping function, and (iii) the introduction of separate scaling of the core-valence and valence-valence Coulombic interactions. Crucially, the parameters of the CVS-QE12 Hamiltonian are obtained via fitting exclusively to highly accurate ab initio vertical core-excitation and ionization energies computed at the CVS-EOM-CCSDT level of theory. The CVS-QE12 Hamiltonian is validated against further benchmark computations and is found to furnish K-edge core vertical excitation and ionization energies exhibiting absolute errors ≤0.5 eV at low computational cost.</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/10.1063/5.0227385\",\"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/10.1063/5.0227385","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
为计算 K 壳核激发和核电离能,定义了一个新参数化的组合密度泛函理论和多参量构型相互作用(DFT/MRCI)哈密顿,称为核价分离(CVS)-QE12。该 CVS 对应于最近报道的 QE8 哈密顿[Costain 等人,J. Chem. Phys, 160, 224106 (2024)],是通过拟合基准质量的 ab initio 数据来确定参数的。CVS-QE12 和 QE8 哈密顿参数的定义与以前的 CVS-DFT/MRCI 参数化有三个主要不同点:(i) 用 QTP17 代替 BHLYP 交换相关函数,以平衡描述核和价激发能;(ii) 采用新的三参数阻尼函数;(iii) 引入核-价和价-价库仑相互作用的单独比例。最重要的是,CVS-QE12 哈密顿参数完全是通过拟合在 CVS-EOM-CCSDT 理论水平上计算出的高精度 ab initio 垂直核激发和电离能而获得的。通过进一步的基准计算验证了 CVS-QE12 哈密顿方程,发现它能以较低的计算成本提供绝对误差小于 0.5 eV 的 K 边核垂直激发和电离能。
A DFT/MRCI Hamiltonian parameterized using only ab initio data. II. Core-excited states.
A newly parameterized combined density functional theory and multi-reference configuration interaction (DFT/MRCI) Hamiltonian, termed core-valence separation (CVS)-QE12, is defined for the computation of K-shell core-excitation and core-ionization energies. This CVS counterpart to the recently reported QE8 Hamiltonian [Costain et al., J. Chem. Phys, 160, 224106 (2024)] is parameterized by fitting to benchmark quality ab initio data. The definition of the CVS-QE12 and QE8 Hamiltonians differ from previous CVS-DFT/MRCI parameterizations in three primary ways: (i) the replacement of the BHLYP exchange-correlation functional with QTP17 to yield a balanced description of both core and valence excitation energies, (ii) the adoption of a new, three-parameter damping function, and (iii) the introduction of separate scaling of the core-valence and valence-valence Coulombic interactions. Crucially, the parameters of the CVS-QE12 Hamiltonian are obtained via fitting exclusively to highly accurate ab initio vertical core-excitation and ionization energies computed at the CVS-EOM-CCSDT level of theory. The CVS-QE12 Hamiltonian is validated against further benchmark computations and is found to furnish K-edge core vertical excitation and ionization energies exhibiting absolute errors ≤0.5 eV at low computational cost.
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.
Topical coverage includes:
Theoretical Methods and Algorithms
Advanced Experimental Techniques
Atoms, Molecules, and Clusters
Liquids, Glasses, and Crystals
Surfaces, Interfaces, and Materials
Polymers and Soft Matter
Biological Molecules and Networks.