Absolutely local occupied and excited molecular orbitals in the 3rd order single excitation perturbation theory for molecular interaction
Absolutely local occupied and excited molecular orbitals in the 3rd order single excitation perturbation theory for molecular interaction
复制标题
分子相互作用三阶单激发微扰理论中的绝对局域占据和激发分子轨道
DOI：
10.1021/jp101483t
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发表时间：
2010
期刊：
影响因子：
2.9
通讯作者：
Suehiro Iwata
中科院分区：
文献类型：
--
作者：
石田豊和;白土東子;成松久;久保田智巳;Suehiro Iwata
开发了在 Hartree−Fock 理论水平上评估分子相互作用能的有效代码。该方法是基于局部投影（LP）分子轨道（MO）的三阶单激发微扰理论。结果表明，通过适当缩放分子轨道积分，即使基组尺寸较小，基组叠加误差也可以得到控制。如果基组包含增强扩散函数，则可以直接评估接近地网校正能量的相互作用能量，而无需缩放，速度与单个超分子 Hartree−Fock 计算一样快。该方法的关键是使用绝对局部占据和激发的MO。利用这些 MO，可以评估电荷转移 (CT) 的量和 CT 项的能量贡献。
The efficient code to evaluate the molecular interaction energy at the Hartree−Fock level of theory is developed. The method is the third-order single excitation perturbation theory based on the locally projected (LP) molecular orbitals (MO). It is shown that with a proper scaling of the molecular orbital integrals the basis set superposition error can be under controll even with a small size of basis sets. If the basis set contains augmented diffuse functions, the interaction energy, close to the counterpoise corrected energy, can be directly evaluated without the scaling, as fast as a single supermolecule Hartree−Fock calculation. The key of the method is to use the absolutely local occupied and excited MOs. With these MOs, the amount of the charge-transfer (CT) and the energy contribution of the CT terms are evaluated.