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

研究成果: 雜誌貢獻期刊論文同行評審

35 引文 斯高帕斯(Scopus)

摘要

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.

原文英語
頁(從 - 到)10705-10712
頁數8
期刊Physical Chemistry Chemical Physics
14
發行號30
DOIs
出版狀態已發佈 - 2012 八月 14

ASJC Scopus subject areas

  • 物理與天文學 (全部)
  • 物理與理論化學

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