title: A long-range-corrected time-dependent density functional theory.
abstract: We apply the long-range correction (LC) scheme for exchange functionals of density functional theory to time-dependent density functional theory (TDDFT) and examine its efficiency in dealing with the serious problems of TDDFT, i.e., the underestimations of Rydberg excitation energies, oscillator strengths, and charge-transfer excitation energies. By calculating vertical excitation energies of typical molecules, it was found that LC-TDDFT gives accurate excitation energies, within an error of 0.5 eV, and reasonable oscillator strengths, while TDDFT employing a pure functional provides 1.5 eV lower excitation energies and two orders of magnitude lower oscillator strengths for the Rydberg excitations. It was also found that LC-TDDFT clearly reproduces the correct asymptotic behavior of the charge-transfer excitation energy of ethylene-tetrafluoroethylene dimer for the long intramolecular distance, unlike a conventional far-nucleus asymptotic correction scheme. It is, therefore, presumed that poor TDDFT results for pure functionals may be due to their lack of a long-range orbital-orbital interaction.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan.
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Tawada
authors.forename: Takao
authors.initials: T
authors.lastname: Tsuneda
authors.forename: Susumu
authors.initials: S
authors.lastname: Yanagisawa
authors.forename: Takeshi
authors.initials: T
authors.lastname: Yanai
authors.forename: Kimihiko
authors.initials: K
authors.lastname: Hirao