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Article
Performance Assessment of Density-Functional Methods for Study of Charge-Transfer Complexes
Journal of Computational Chemistry (2003)
  • M.-S. Liao
  • Y. Lu
  • Steve Scheiner, Utah State University
Abstract

Various density functionals are applied to a number of weakly bound intermolecular π–π charge-transfer (CT) complexes. Most functionals, including the recently developed mPWPW91 and mPW1PW91, grossly underestimate experimental excitation energies; good agreement is obtained only with the half-and-half hybrid BH&HLYP functional. PW91PW91 provides the best agreement with intermolecular distances measured in crystal, while the BH&HLYP values are about 0.1 Å too long. Various hybrid functionals with nonlocal exchange correction provide binding energies that compare favorably with the experimental heats of formation measured in solution.

Keywords
  • performance,
  • assessment,
  • density,
  • functional,
  • methods,
  • study,
  • charge,
  • transfer,
  • complexes
Disciplines
Publication Date
January 1, 2003
Citation Information
Performance Assessment of Density-Functional Methods for Study of Charge-Transfer Complexes M.-S. Liao, Y. Lu, S. Scheiner J. Comput. Chem. 2003 24 623-631