Article
Performance Assessment of Density-Functional Methods for Study of Charge-Transfer Complexes
Journal of Computational Chemistry
(2003)
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