电荷转移对分子间相互作用能贡献的非微扰成对可加分析
A Non-Perturbative Pairwise-Additive Analysis of Charge Transfer Contributions to Intermolecular Interaction Energies
摘要：
基于绝对定域分子轨道（ALMO）的能量分解分析（EDA）将分子之间的相互作用能分解成物理上可解释的组分，如几何畸变、冻结相互作用、极化和电荷转移（CT，有时也称为电荷离域）相互作用。在这项工作中，一个数值精确的计划，分解CT相互作用能成成对的加性条款介绍了ALMO-EDA使用密度泛函理论。与微扰成对电荷分解分析不同，新方法不会分解为强相互作用系统，也不会在分解的能量分量中显示出显着的交换相关函数依赖性。与CT相关的能量降低和电荷流都可以分解。互补占据虚轨道对（COVP），捕获占主导地位的供体和受体CT轨道获得新的分解。它适用于具有不同类型相互作用的系统，包括DNA碱基对，硼烷-氨加合物和过渡金属六羰基化合物。虽然与大多数现有的理解CT在这些系统中的性质是一致的，但结果也揭示了一些新的见解，供体-受体相互作用趋势的起源。
英文摘要：
Energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs) decomposes the interaction energy between molecules into physically interpretable components like geometry distortion, frozen interactions, polarization, and charge transfer (CT, also sometimes called charge delocalization) interactions. In this work, a numerically exact scheme to decompose the CT interaction energy into pairwise additive terms is introduced for the ALMO-EDA using density functional theory. Unlike perturbative pairwise charge-decomposition analysis, the new approach does not break down for strongly interacting systems, or show significant exchange-correlation functional dependence in the decomposed energy components. Both the energy lowering and the charge flow associated with CT can be decomposed. Complementary occupied-virtual orbital pairs (COVPs) that capture the dominant donor and acceptor CT orbitals are obtained for the new decomposition. It is applied to systems with different types of interactions including DNA base-pairs, borane-ammonia adducts, and transition metal hexacarbonyls. While consistent with most existing understanding of the nature of CT in these systems, the results also reveal some new insights into the origin of trends in donor-acceptor interactions.
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