Ciofini I, Adamo C, Chermette H
Ecole Nationale Supérieure de Chimie de Paris (ENSCP), Laboratoire d'Electrochimie et Chimie Analytique, Unité Mixte de Recherche (UMR) Centre National de la Recherche Scientifique (CNRS)-ENSCP n 7575, F-75231 Paris 05, France.
J Chem Phys. 2005 Sep 22;123(12):121102. doi: 10.1063/1.2047447.
The calculation of the bond-length alternation (BLA) in trans-polyacetylene has been chosen as benchmark to emphasize the effect of the self-interaction error within density-functional theory (DFT). In particular, the BLA of increasingly long acetylene oligomers has been computed using the Møller-Plesset wave-function method truncated at the second order and several DFT models. While local-density approximation (LDA) or generalized gradient corrected (GGA) functionals strongly underestimate the BLA, approaches including self-interaction corrections (SIC) provide significant improvements. Indeed, the simple averaged-density SIC scheme (ADSIC), recently proposed by Legrand et al. [J. Phys. B 35, 1115 (2002)], provides better results for the structure of large oligomers than the more complex approach of Krieger et al. [Phys. Rev. A 45, 101 (1992)]. The ADSIC method is particularly promising since both the exchange-correlation energy and potential are improved with respect to standard LDA/GGA using a physically appealing correction, through a different route than the more popular approach through the Hartree-Fock exchange inclusion within the hybrid functionals.
选择对反式聚乙炔中键长交替(BLA)的计算作为基准,以强调密度泛函理论(DFT)中自相互作用误差的影响。特别是,使用二阶截断的Møller-Plesset波函数方法和几种DFT模型计算了越来越长的乙炔低聚物的BLA。虽然局域密度近似(LDA)或广义梯度校正(GGA)泛函强烈低估了BLA,但包括自相互作用校正(SIC)的方法有显著改进。实际上,勒格朗等人[《物理学报B》35, 1115 (2002)]最近提出的简单平均密度SIC方案(ADSIC),对于大低聚物的结构,比克里格等人[《物理评论A》45, 101 (1992)]更复杂的方法能给出更好的结果。ADSIC方法特别有前景,因为与通过在杂化泛函中包含Hartree-Fock交换这种更流行的方法不同,通过一种具有物理吸引力的校正,相对于标准LDA/GGA,交换关联能和势都得到了改进。