Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

Yi Gao, Xiao C Zeng

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Møller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems.

Original languageEnglish (US)
Article number386220
JournalJournal of Physics Condensed Matter
Volume19
Issue number38
DOIs
StatePublished - Sep 26 2007

Fingerprint

organic materials
Hydrogen
Local density approximation
Metals
Adsorption
adsorption
Density functional theory
hydrogen
approximation
metals
Binding energy
density functional theory
gradients
binding energy
Molecular orbitals
organic solids
predictions
molecular orbitals
costs
perturbation

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials. / Gao, Yi; Zeng, Xiao C.

In: Journal of Physics Condensed Matter, Vol. 19, No. 38, 386220, 26.09.2007.

Research output: Contribution to journalArticle

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abstract = "We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio M{\o}ller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems.",
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