Assessment of density functional approximations for the hemibonded structure of the water dimer radical cation

Piin Ruey Pan, You Sheng Lin, Ming Kang Tsai, Jer Lai Kuo, Jeng Da Chai

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Due to the severe self-interaction errors associated with some density functional approximations, conventional density functionals often fail to dissociate the hemibonded structure of the water dimer radical cation (H 2O) 2 + into the correct fragments: H 2O and H 2O +. Consequently, the binding energy of the hemibonded structure (H 2O) 2 + is not well-defined. For a comprehensive comparison of different functionals for this system, we propose three criteria: (i) the binding energies, (ii) the relative energies between the conformers of the water dimer radical cation, and (iii) the dissociation curves predicted by different functionals. The long-range corrected (LC) double-hybrid functional, ωB97X-2(LP) [J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2009, 131, 174105], is shown to perform reasonably well based on these three criteria. Reasons that LC hybrid functionals generally work better than conventional density functionals for hemibonded systems are also explained in this work.

Original languageEnglish
Pages (from-to)10705-10712
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number30
DOIs
Publication statusPublished - 2012 Aug 14

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Binding energy
functionals
Dimers
Cations
dimers
cations
Water
approximation
water
binding energy
fragments
dissociation
curves
interactions
energy

ASJC Scopus subject areas

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

Cite this

Assessment of density functional approximations for the hemibonded structure of the water dimer radical cation. / Pan, Piin Ruey; Lin, You Sheng; Tsai, Ming Kang; Kuo, Jer Lai; Chai, Jeng Da.

In: Physical Chemistry Chemical Physics, Vol. 14, No. 30, 14.08.2012, p. 10705-10712.

Research output: Contribution to journalArticle

Pan, Piin Ruey ; Lin, You Sheng ; Tsai, Ming Kang ; Kuo, Jer Lai ; Chai, Jeng Da. / Assessment of density functional approximations for the hemibonded structure of the water dimer radical cation. In: Physical Chemistry Chemical Physics. 2012 ; Vol. 14, No. 30. pp. 10705-10712.
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