When Hartree-Fock exchange admixture lowers DFT-predicted barrier heights

Natural bond orbital analyses and implications for catalysis

Andrew Mahler, Benjamin G. Janesko, Salvador Moncho Escriva, Edward Brothers

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The conventional wisdom in density functional theory (DFT) is that standard approximations systematically underestimate chemical reaction barrier heights and that exact (Hartree-Fock-like, HF) exchange admixture improves this. This conventional wisdom is inconsistent with the good performance of functionals without HF exchange for many reactions on metal catalyst surfaces. We have studied several "anomalous" gas-phase reactions where this conventional wisdom is upended, and a HF exchange admixture decreases or does not affect the predicted barrier heights [Mahler et al., J. Chem. Phys. 146, 234103 (2017)]. Here we show how natural bond orbital analyses can help identify and explain some factors that produce anomalous barriers. Applications to pnictogen inversion, standard benchmark reaction barrier datasets, and a model Grubbs catalyst illustrate the utility of this approach. This approach is expected to aid DFT users in choosing appropriate functionals, and aid DFT developers in devising DFT approximations generally applicable to catalysis.

Original languageEnglish
Article number244106
JournalJournal of Chemical Physics
Volume148
Issue number24
DOIs
Publication statusPublished - 28 Jun 2018

Fingerprint

admixtures
Catalysis
catalysis
Density functional theory
density functional theory
orbitals
functionals
catalysts
Catalysts
photographic developers
approximation
Chemical reactions
chemical reactions
Gases
Metals
inversions
vapor phases
metals

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

@article{1c3a308b9aa647738c1d48b35e14fa4d,
title = "When Hartree-Fock exchange admixture lowers DFT-predicted barrier heights: Natural bond orbital analyses and implications for catalysis",
abstract = "The conventional wisdom in density functional theory (DFT) is that standard approximations systematically underestimate chemical reaction barrier heights and that exact (Hartree-Fock-like, HF) exchange admixture improves this. This conventional wisdom is inconsistent with the good performance of functionals without HF exchange for many reactions on metal catalyst surfaces. We have studied several {"}anomalous{"} gas-phase reactions where this conventional wisdom is upended, and a HF exchange admixture decreases or does not affect the predicted barrier heights [Mahler et al., J. Chem. Phys. 146, 234103 (2017)]. Here we show how natural bond orbital analyses can help identify and explain some factors that produce anomalous barriers. Applications to pnictogen inversion, standard benchmark reaction barrier datasets, and a model Grubbs catalyst illustrate the utility of this approach. This approach is expected to aid DFT users in choosing appropriate functionals, and aid DFT developers in devising DFT approximations generally applicable to catalysis.",
author = "Andrew Mahler and Janesko, {Benjamin G.} and {Moncho Escriva}, Salvador and Edward Brothers",
year = "2018",
month = "6",
day = "28",
doi = "10.1063/1.5032218",
language = "English",
volume = "148",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "24",

}

TY - JOUR

T1 - When Hartree-Fock exchange admixture lowers DFT-predicted barrier heights

T2 - Natural bond orbital analyses and implications for catalysis

AU - Mahler, Andrew

AU - Janesko, Benjamin G.

AU - Moncho Escriva, Salvador

AU - Brothers, Edward

PY - 2018/6/28

Y1 - 2018/6/28

N2 - The conventional wisdom in density functional theory (DFT) is that standard approximations systematically underestimate chemical reaction barrier heights and that exact (Hartree-Fock-like, HF) exchange admixture improves this. This conventional wisdom is inconsistent with the good performance of functionals without HF exchange for many reactions on metal catalyst surfaces. We have studied several "anomalous" gas-phase reactions where this conventional wisdom is upended, and a HF exchange admixture decreases or does not affect the predicted barrier heights [Mahler et al., J. Chem. Phys. 146, 234103 (2017)]. Here we show how natural bond orbital analyses can help identify and explain some factors that produce anomalous barriers. Applications to pnictogen inversion, standard benchmark reaction barrier datasets, and a model Grubbs catalyst illustrate the utility of this approach. This approach is expected to aid DFT users in choosing appropriate functionals, and aid DFT developers in devising DFT approximations generally applicable to catalysis.

AB - The conventional wisdom in density functional theory (DFT) is that standard approximations systematically underestimate chemical reaction barrier heights and that exact (Hartree-Fock-like, HF) exchange admixture improves this. This conventional wisdom is inconsistent with the good performance of functionals without HF exchange for many reactions on metal catalyst surfaces. We have studied several "anomalous" gas-phase reactions where this conventional wisdom is upended, and a HF exchange admixture decreases or does not affect the predicted barrier heights [Mahler et al., J. Chem. Phys. 146, 234103 (2017)]. Here we show how natural bond orbital analyses can help identify and explain some factors that produce anomalous barriers. Applications to pnictogen inversion, standard benchmark reaction barrier datasets, and a model Grubbs catalyst illustrate the utility of this approach. This approach is expected to aid DFT users in choosing appropriate functionals, and aid DFT developers in devising DFT approximations generally applicable to catalysis.

UR - http://www.scopus.com/inward/record.url?scp=85049307189&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85049307189&partnerID=8YFLogxK

U2 - 10.1063/1.5032218

DO - 10.1063/1.5032218

M3 - Article

VL - 148

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 24

M1 - 244106

ER -