View in EDS

Insights Into Density Functional Performance From a Main‐Group and Transition‐Metal Molecular Benchmark.

Saved in:
Bibliographic Details
Title: Insights Into Density Functional Performance From a Main‐Group and Transition‐Metal Molecular Benchmark.
Authors: Liu, Yiwei1 (AUTHOR) yiweiliu@sit.edu.cn, Wei, Lijie1 (AUTHOR), Tao, Shuai1 (AUTHOR), Wu, Yichu1 (AUTHOR), Wu, Fanhong1 (AUTHOR), Wang, Ying2 (AUTHOR) wangyin@hunnu.edu.cn, He, Xiao3,4,5 (AUTHOR) xiaohe@phy.ecnu.edu.cn
Source: Journal of Computational Chemistry. 5/5/2026, Vol. 47 Issue 12, p1-11. 11p.
Subjects: Density functionals, Transition metal compounds, Activation energy, Scission (Chemistry), Density functional theory, Molecular energy levels (Quantum mechanics)
Abstract: Density functional theory (DFT) is widely used for modeling molecular energetics, yet the accuracy of density functionals strongly depends on the chemical environment, making reliable functional selection across diverse applications. To facilitate the rational selection of functionals, we systematically assess the performance of 26 density functionals across six representative classes of molecular energetics, including reaction barriers, polar σ‐bond dissociation, ionization energies, metal–ligand dissociation, catalytic barrier heights, and strongly correlated 3d transition‐metal complexes. By jointly analyzing datasets spanning both main‐group and transition‐metal chemistry, this work provides a cross‐domain assessment of functional performance across chemically distinct regimes. Our results indicate that functional transferability between these two domains tends to be constrained, with relatively few hybrid meta‐NGAs and hybrid meta‐GGAs (e.g., CF22D, PW6B95‐D3(BJ)) demonstrating comparatively balanced accuracy across diverse datasets, while multi‐reference cases remain challenging for all functionals considered. The dataset‐specific analysis provides practical insights for functional selection: HSE06‐D3(BJ), PBE‐D3(BJ), and M06‐2X‐D3(0) functionals perform well for main‐group reaction barriers, while CF22D, M06‐D3(0), M06 and MN15 functionals are more reliable for polar bond dissociation. For transition‐metal energetics, CF22D, PW6B95‐D3(BJ), and HSE06‐D3(BJ) functionals offer robust performance. Overall, this study delineates the strengths and limitations of modern density‐functional approximations and offers data‐driven guidance for functional selection in heterogeneous molecular problems. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 193490609
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Insights Into Density Functional Performance From a Main‐Group and Transition‐Metal Molecular Benchmark.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Liu%2C+Yiwei%22">Liu, Yiwei</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> yiweiliu@sit.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Wei%2C+Lijie%22">Wei, Lijie</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Tao%2C+Shuai%22">Tao, Shuai</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wu%2C+Yichu%22">Wu, Yichu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wu%2C+Fanhong%22">Wu, Fanhong</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wang%2C+Ying%22">Wang, Ying</searchLink><relatesTo>2</relatesTo> (AUTHOR)<i> wangyin@hunnu.edu.cn</i><br /><searchLink fieldCode="AR" term="%22He%2C+Xiao%22">He, Xiao</searchLink><relatesTo>3,4,5</relatesTo> (AUTHOR)<i> xiaohe@phy.ecnu.edu.cn</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+Computational+Chemistry%22">Journal of Computational Chemistry</searchLink>. 5/5/2026, Vol. 47 Issue 12, p1-11. 11p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink><br /><searchLink fieldCode="DE" term="%22Transition+metal+compounds%22">Transition metal compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Activation+energy%22">Activation energy</searchLink><br /><searchLink fieldCode="DE" term="%22Scission+%28Chemistry%29%22">Scission (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+energy+levels+%28Quantum+mechanics%29%22">Molecular energy levels (Quantum mechanics)</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Density functional theory (DFT) is widely used for modeling molecular energetics, yet the accuracy of density functionals strongly depends on the chemical environment, making reliable functional selection across diverse applications. To facilitate the rational selection of functionals, we systematically assess the performance of 26 density functionals across six representative classes of molecular energetics, including reaction barriers, polar σ‐bond dissociation, ionization energies, metal–ligand dissociation, catalytic barrier heights, and strongly correlated 3d transition‐metal complexes. By jointly analyzing datasets spanning both main‐group and transition‐metal chemistry, this work provides a cross‐domain assessment of functional performance across chemically distinct regimes. Our results indicate that functional transferability between these two domains tends to be constrained, with relatively few hybrid meta‐NGAs and hybrid meta‐GGAs (e.g., CF22D, PW6B95‐D3(BJ)) demonstrating comparatively balanced accuracy across diverse datasets, while multi‐reference cases remain challenging for all functionals considered. The dataset‐specific analysis provides practical insights for functional selection: HSE06‐D3(BJ), PBE‐D3(BJ), and M06‐2X‐D3(0) functionals perform well for main‐group reaction barriers, while CF22D, M06‐D3(0), M06 and MN15 functionals are more reliable for polar bond dissociation. For transition‐metal energetics, CF22D, PW6B95‐D3(BJ), and HSE06‐D3(BJ) functionals offer robust performance. Overall, this study delineates the strengths and limitations of modern density‐functional approximations and offers data‐driven guidance for functional selection in heterogeneous molecular problems. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Computational Chemistry is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=193490609
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1002/jcc.70388
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 11
        StartPage: 1
    Subjects:
      – SubjectFull: Density functionals
        Type: general
      – SubjectFull: Transition metal compounds
        Type: general
      – SubjectFull: Activation energy
        Type: general
      – SubjectFull: Scission (Chemistry)
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Molecular energy levels (Quantum mechanics)
        Type: general
    Titles:
      – TitleFull: Insights Into Density Functional Performance From a Main‐Group and Transition‐Metal Molecular Benchmark.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Liu, Yiwei
      – PersonEntity:
          Name:
            NameFull: Wei, Lijie
      – PersonEntity:
          Name:
            NameFull: Tao, Shuai
      – PersonEntity:
          Name:
            NameFull: Wu, Yichu
      – PersonEntity:
          Name:
            NameFull: Wu, Fanhong
      – PersonEntity:
          Name:
            NameFull: Wang, Ying
      – PersonEntity:
          Name:
            NameFull: He, Xiao
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 05
              M: 05
              Text: 5/5/2026
              Type: published
              Y: 2026
          Identifiers:
            – Type: issn-print
              Value: 01928651
          Numbering:
            – Type: volume
              Value: 47
            – Type: issue
              Value: 12
          Titles:
            – TitleFull: Journal of Computational Chemistry
              Type: main
ResultId 1