A long-range-corrected time-dependent density functional theory
A long-range-corrected time-dependent density functional theory
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DOI：
10.1063/1.1688752
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发表时间：
2004-05-08
影响因子：
4.4
通讯作者：
Hirao, K
中科院分区：
文献类型：
--
作者：
Tawada, Y;Tsuneda, T;Hirao, K
我们将密度泛函理论中交换泛函的长程修正（LC）方案应用到含时密度泛函理论（TDDFT）中，并考察了它在处理TDDFT中的严重问题时的效率，即，里德堡激发能、振子强度和电荷转移激发能的低估。通过计算典型分子的垂直激发能，发现LC-TDDFT给出了精确的激发能，误差在0.5eV以内，振子强度合理，而TDDFT采用纯泛函，对Rydberg激发提供了低1.5eV的激发能和低两个数量级的振子强度.还发现，LC-TDDFT清楚地再现了正确的渐近行为的电荷转移激发能量的乙烯-α-二聚体的长的分子内距离，不同于传统的远核渐近校正方案。因此，可以推测，纯泛函的TDDFT结果不佳可能是由于它们缺乏长程轨道-轨道相互作用。(C)2004年，美国物理学会。
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. (C) 2004 American Institute of Physics.