A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems.
A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems.
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DOI：
10.1063/1.4919943
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发表时间：
2015-01
期刊：
影响因子：
--
通讯作者：
M. Raupach;R. Tonner
中科院分区：
文献类型：
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作者：
M. Raupach;R. Tonner
描述了基于密度泛函理论 Kohn-Sham 方法的扩展系统的新周期能量分解分析 (pEDA) 方案的开发和首次应用。 pEDA 将两个片段之间的键能（例如，表面上分子的吸附能）分解为几个明确定义的术语：制备、静电、泡利排斥和轨道弛豫能。通过成对方案考虑色散相互作用对此进行了补充。对先前实现的一个重大扩展 [Philipsen 和 Baerends，J. Phys。化学。 B 110, 12470 (2006)]在于静电和泡利的单独讨论以及色散项的添加。这里提出的基于原子轨道的实现的 pEDA 可以处理 0D 到 3D 系统的受限和非受限碎片，考虑周期性边界条件，有或没有确定碎片占用。对于后一种情况，启用倒数空间采样。新方法给出的结果与已建立的分子系统方案相当，并且在基组 (TZ2P)、积分精度和 k 空间采样方面表现出良好的收敛性。选择表面吸附复合物的四种典型键合方案来突出代表绝缘（MgO（001）上的 CO）、金属（M（001）上的 H2，M = Pd、Cu）和半导体（Si（001）上的 CO 和 C2H2）基材的方法的性能。这些示例涵盖了不同的基材以及从弱相互作用到共价（共享电子和供体受体）键合的键合场景。所得出的结果使人们相信，pEDA 将成为未来分析表面吸附物键合的强大工具，从而能够将离子键合和共价键合、供体-受体相互作用、空间排斥等概念转移到扩展系统中。
The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H2 on M(001), M = Pd, Cu), and semiconducting (CO and C2H2 on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.