Energy decomposition analyses for many-body interaction and applications to water complexes
Energy decomposition analyses for many-body interaction and applications to water complexes
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DOI：
10.1021/jp960694r
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发表时间：
1996-08-22
影响因子：
--
通讯作者：
Gordon, MS
中科院分区：
文献类型：
--
作者：
Chen, W;Gordon, MS
提出了Hartree-Fock近似下多体相互作用能分解的两种算法，这两种算法是两体Kitaura-Morokuma（KM）分析和约化变分空间自洽场（RVS SCF）方法的推广，将相互作用能分解为静电、交换、极化和电荷转移四个分量。最佳的水二聚体，三聚体，四聚体的Hartree-Fock相互作用能进行了分析，在两个，三个，和四体条款，这些单独的组件。对Tomasi提出的交换和电荷转移组分进行了平衡计算，以估计基组叠加误差。结果表明，在不同基组的优化结构下，水三聚体和水四聚体的三体非加性项主要由极化分量和电荷转移分量决定，而水四聚体的四体非加性项很小.当轨道相互作用较强时，RVS SCF能量分量的对应波函数服从泡利不相容原理，比KM分析中的对应波函数表现得更好。
Two algorithms for many-body interaction energy decomposition within the Hartree-Fock approximation an presented, These two schemes, which are extensions of the two-body Kitaura-Morokuma (KM) analysis and the reduced variational space self-consistent-field(RVS SCF) method, decompose the interaction energy into electrostatic, exchange, polarization, and charge transfer components. The Hartree-Fock interaction energies for the optimum water dimer, trimer, and tetramer were analyzed in terms of two-, three-, and four-body terms of these individual components. Counterpoise calculations of the exchange and charge transfer components proposed by Tomasi were performed to estimate the basis set superposition errors. The results show that the three-body nonadditive terms of water trimer and tetramer are dominated by the polarization and charge transfer components at their optimized structures with various basis sets and that the four-body term of water tetramer is very small. The RVS SCF energy components, whose corresponding wave functions obey the Pauli exclusion principle, are better behaved than their counterparts in the KM analysis when the orbital interactions are strong.