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A Molecular "Thermometer" for Measuring Effective Non‐Local Exchange.

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Title: A Molecular "Thermometer" for Measuring Effective Non‐Local Exchange.
Authors: Grimme, Stefan1 (AUTHOR) grimme@thch.uni‐bonn.de, Müller, Marcel1,2,3 (AUTHOR), Froitzheim, Thomas1 (AUTHOR), Hansen, Andreas1 (AUTHOR)
Source: Journal of Computational Chemistry. 6/30/2026, Vol. 47 Issue 17, p1-11. 11p.
Subjects: Isomerization, Hartree-Fock approximation, Molecules, Density functional theory, Ab initio quantum chemistry methods, Thermochemistry, Ethynyl benzene
Abstract: Non‐local exchange (NLX) is a key ingredient for accurate density functional calculations, but its effective strength is often hard to quantify beyond simple global hybrids. To this end, we introduce a molecular probe based on the isomerization of hexaethynylbenzene to carbo‐benzene, a reaction with exceptional sensitivity to exchange effects. Using the isomerization energy, we define a simple relative measure, tX$$ {t}_{\mathrm{X}} $$, that gauges the effective NLX of a method on a scale ranging from 0 for the local density approximation to 100 for Hartree‐Fock. Across a broad set of density functional approximations, tX$$ {t}_{\mathrm{X}} $$ closely tracks the formal Hartree‐Fock exchange content of global hybrids, while revealing that most common GGAs, meta‐GGAs, and global hybrids still provide too little effective exchange. Several range‐separated hybrid, double hybrid, and some local hybrid functionals perform much better and closely approach the near‐basis‐set‐limit coupled‐cluster reference value of tX=60$$ {t}_{\mathrm{X}}=60 $$. The tX$$ {t}_{\mathrm{X}} $$ values of various semiempirical quantum mechanical and machine‐learned interatomic potential methods indicate that they empirically account for NLX effects to a varying degree. Thus, the proposed reaction serves as a compact thermochemical benchmark for assessing and developing methods that aim to reliably describe NLX. [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
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Header DbId: egs
DbLabel: Engineering Source
An: 194973517
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
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  Label: Title
  Group: Ti
  Data: A Molecular "Thermometer" for Measuring Effective Non‐Local Exchange.
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  Data: <searchLink fieldCode="AR" term="%22Grimme%2C+Stefan%22">Grimme, Stefan</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> grimme@thch.uni‐bonn.de</i><br /><searchLink fieldCode="AR" term="%22Müller%2C+Marcel%22">Müller, Marcel</searchLink><relatesTo>1,2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Froitzheim%2C+Thomas%22">Froitzheim, Thomas</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Hansen%2C+Andreas%22">Hansen, Andreas</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Computational+Chemistry%22">Journal of Computational Chemistry</searchLink>. 6/30/2026, Vol. 47 Issue 17, p1-11. 11p.
– Name: Subject
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  Data: <searchLink fieldCode="DE" term="%22Isomerization%22">Isomerization</searchLink><br /><searchLink fieldCode="DE" term="%22Hartree-Fock+approximation%22">Hartree-Fock approximation</searchLink><br /><searchLink fieldCode="DE" term="%22Molecules%22">Molecules</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Ab+initio+quantum+chemistry+methods%22">Ab initio quantum chemistry methods</searchLink><br /><searchLink fieldCode="DE" term="%22Thermochemistry%22">Thermochemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Ethynyl+benzene%22">Ethynyl benzene</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Non‐local exchange (NLX) is a key ingredient for accurate density functional calculations, but its effective strength is often hard to quantify beyond simple global hybrids. To this end, we introduce a molecular probe based on the isomerization of hexaethynylbenzene to carbo‐benzene, a reaction with exceptional sensitivity to exchange effects. Using the isomerization energy, we define a simple relative measure, tX$$ {t}_{\mathrm{X}} $$, that gauges the effective NLX of a method on a scale ranging from 0 for the local density approximation to 100 for Hartree‐Fock. Across a broad set of density functional approximations, tX$$ {t}_{\mathrm{X}} $$ closely tracks the formal Hartree‐Fock exchange content of global hybrids, while revealing that most common GGAs, meta‐GGAs, and global hybrids still provide too little effective exchange. Several range‐separated hybrid, double hybrid, and some local hybrid functionals perform much better and closely approach the near‐basis‐set‐limit coupled‐cluster reference value of tX=60$$ {t}_{\mathrm{X}}=60 $$. The tX$$ {t}_{\mathrm{X}} $$ values of various semiempirical quantum mechanical and machine‐learned interatomic potential methods indicate that they empirically account for NLX effects to a varying degree. Thus, the proposed reaction serves as a compact thermochemical benchmark for assessing and developing methods that aim to reliably describe NLX. [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.)
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1002/jcc.70436
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 11
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    Subjects:
      – SubjectFull: Isomerization
        Type: general
      – SubjectFull: Hartree-Fock approximation
        Type: general
      – SubjectFull: Molecules
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Ab initio quantum chemistry methods
        Type: general
      – SubjectFull: Thermochemistry
        Type: general
      – SubjectFull: Ethynyl benzene
        Type: general
    Titles:
      – TitleFull: A Molecular "Thermometer" for Measuring Effective Non‐Local Exchange.
        Type: main
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          Name:
            NameFull: Grimme, Stefan
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            NameFull: Müller, Marcel
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            NameFull: Froitzheim, Thomas
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            NameFull: Hansen, Andreas
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            – D: 30
              M: 06
              Text: 6/30/2026
              Type: published
              Y: 2026
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              Value: 47
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            – TitleFull: Journal of Computational Chemistry
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