A long-range-corrected time-dependent density functional theory

Journal of Chemical Physics - Tập 120 Số 18 - Trang 8425-8433 - 2004
Yuko Tawada1, Takao Tsuneda1, Susumu Yanagisawa1, Takeshi Yanai2, Kimihiko Hirao1
1Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
2Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6367

Tóm tắt

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.

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Thông tin xuất bản

Journal of Chemical Physics

Tập 120 Số 18

8425-8433

Thông tin tác giả