Energy Decomposition Scheme Based on the Generalized Kohn鈥揝ham Scheme

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• 作者：Peifeng Su ; Zhen Jiang ; Zuochang Chen ; Wei Wu
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：April 3, 2014
• 年：2014
• 卷：118
• 期：13
• 页码：2531-2542
• 全文大小：360K
• 年卷期：v.118,no.13(April 3, 2014)
• ISSN：1520-5215

文摘

In this paper, a new energy decomposition analysis scheme based on the generalized Kohn鈥揝ham (GKS) and the localized molecular orbital energy decomposition analysis (LMO-EDA) scheme, named GKS-EDA, is proposed. The GKS-EDA scheme has a wide range of DFT functional adaptability compared to LMO-EDA. In the GKS-EDA scheme, the exchange, repulsion, and polarization terms are determined by DFT orbitals; the correlation term is defined as the difference of the GKS correlation energy from monomers to supermolecule. Using the new definition, the GKS-EDA scheme avoids the error of LMO-EDA which comes from the separated treatment of E<sub>Xsub> and E<sub>Csub> functionals. The scheme can perform analysis both in the gas and in the condensed phases with most of the popular DFT functionals, including LDA, GGA, meta-GGA, hybrid GGA/meta-GGA, double hybrid, range-separated (long-range correction), and dispersion correction. By the GKS-EDA scheme, the DFT functionals assessment for hydrogen bonding, vdW interaction, symmetric radical cation, charge-transfer, and metal鈥搇igand interaction is performed.