Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies
Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies
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DOI：
10.1063/1.4942921
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发表时间：
2016-03-21
影响因子：
4.4
通讯作者：
Head-Gordon, Martin
中科院分区：
文献类型：
--
作者：
Horn, Paul R.;Mao, Yuezhi;Head-Gordon, Martin
在Kohn-Sham密度泛函理论计算的能量分解分析中，所谓的冻结（或预极化）相互作用能包含来自永久静电，色散和泡利排斥的贡献。区分它们的标准经典方法受到几个众所周知的限制。我们引入了一种替代方案，该方案自始至终采用有效的反对称电子波函数，并基于对初始超系统波函数的单个片段贡献的识别，由能量最优性准则确定。分析了初始超系统波函数形成时单个片段的密度变形，以及新术语和经典术语的距离依赖性，这些测试用例包括氖二聚体、氨硼烷、水- na +、水- cl -和萘二聚体。(C) 2016 AIP出版有限责任公司
In energy decomposition analysis of Kohn-Sham density functional theory calculations, the so-called frozen (or pre-polarization) interaction energy contains contributions from permanent electrostatics, dispersion, and Pauli repulsion. The standard classical approach to separate them suffers from several well-known limitations. We introduce an alternative scheme that employs valid antisymmetric electronic wavefunctions throughout and is based on the identification of individual fragment contributions to the initial supersystem wavefunction as determined by an energetic optimality criterion. The density deformations identified with individual fragments upon formation of the initial supersystem wavefunction are analyzed along with the distance dependence of the new and classical terms for test cases that include the neon dimer, ammonia borane, water-Na+, water-Cl-, and the naphthalene dimer. (C) 2016 AIP Publishing LLC.