Glendening Eric D
Department of Chemistry, Indiana State University, Terre Haute, Indiana 47809, USA.
J Phys Chem A. 2005 Dec 29;109(51):11936-40. doi: 10.1021/jp058209s.
Natural energy decomposition analysis (NEDA) is a method for partitioning molecular interaction energies into physically meaningful components, including electrical interaction, charge transfer, and core repulsions. The method is a numerically stable procedure that was originally developed for analyzing Hartree-Fock (HF) wave functions based on the localized orbital description of natural bond orbital analysis. In this work, we extend NEDA to treat charge densities from density functional theory (DFT) calculations, replacing the intermolecular exchange (EX) component of the HF analysis with an exchange-correlation (XC) component. DFT/NEDA is applied to hydrogen bonding interactions and cooperative effects in water clusters. Electrical interactions and charge transfer contribute importantly to hydrogen bonding. Comparison of HF and DFT results reveals that the exchange and correlation effects of DFT slightly enhance the extent of charge transfer and core repulsions in the water clusters. Cooperative stabilization of the cyclic water trimer and tetramer is considered by performing a many-body expansion of the interaction energy. Natural energy decomposition analysis of this expansion suggests that charge transfer is the leading source of cooperative stabilization. Polarization effects have only marginal influence on cooperativity.
自然能量分解分析（NEDA）是一种将分子相互作用能划分为具有物理意义的组分的方法，这些组分包括电相互作用、电荷转移和核心排斥作用。该方法是一种数值稳定的程序，最初是基于自然键轨道分析的定域轨道描述而开发，用于分析哈特里-福克（HF）波函数。在本工作中，我们将NEDA扩展至处理密度泛函理论（DFT）计算得到的电荷密度，用交换相关（XC）组分取代HF分析中的分子间交换（EX）组分。DFT/NEDA被应用于水簇中的氢键相互作用和协同效应。电相互作用和电荷转移对氢键形成有重要贡献。HF和DFT结果的比较表明，DFT的交换和相关效应略微增强了水簇中电荷转移和核心排斥的程度。通过对相互作用能进行多体展开来考虑环状三聚体和四聚体水的协同稳定性。对该展开式进行自然能量分解分析表明，电荷转移是协同稳定的主要来源。极化效应仅对协同性有微弱影响。
