基于伪谱法的修正区域自相互作用校正方法。

Modified regional self-interaction correction method based on the pseudospectral method.

机构信息

Next-generation Molecular Theory Unit, Advanced Science Institute, RIKEN, Saitama 351-0198, Japan.

出版信息

J Phys Chem A. 2010 Aug 26;114(33):8521-8. doi: 10.1021/jp909915d.

PMID:20099795

Abstract

A modification of the regional self-interaction correction (RSIC) scheme (Tsuneda et al., J. Comput. Chem. 2003, 24, 1592), pseudospectral RSIC (PSRSIC), is proposed to eliminate the self-interaction errors (SIEs) especially in core regions. PSRSIC reduces the SIEs by substituting the HF exchange energy density calculated with the use of the pseudospectral technique for the exchange energy in the SI-domain region. PSRSIC is combined with the long-range correction (LC) scheme. TDDFT calculations with LC-PSRSIC yield all of the core-, valence-, Rydberg-, and charge-transfer-excitation energies with reasonable accuracy. Core-ionization energies are also well-reproduced by LC-PSRSIC.

摘要

提出了一种改进的局域自相互作用修正（RSIC）方案（Tsuneda 等人，J. Comput. Chem. 2003, 24, 1592），即赝谱 RSIC（PSRSIC），以消除特别是在核心区域的自相互作用误差（SIEs）。PSRSIC 通过用赝谱技术计算的 HF 交换能密度替代 SI 域区域中的交换能，从而减少 SIE。PSRSIC 与长程校正（LC）方案结合使用。带有 LC-PSRSIC 的 TDDFT 计算以合理的精度得出了所有的芯、价、Rydberg 和电荷转移激发能。LC-PSRSIC 也很好地再现了芯离子化能。