Interaction energy of large molecules from restrained denominator MP2-F12
Interaction energy of large molecules from restrained denominator MP2-F12
复制标题
来自约束分母 MP2-F12 的大分子相互作用能
DOI：
10.1021/ct500738g
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
and S. Ten-no
中科院分区：
文献类型：
--
作者：
Y.-y. Ohnishi;K. Ishimura;and S. Ten-no
提出了一个新的二阶Møller-Plesset多体微扰理论（MP2）的单参数修正方案，以正确计算大π-π色散相互作用体系以及氢键和σ-σ色散相互作用体系的分子间相互作用能.该方案限制了MP2相关能表达式的分母，因为在大π-π堆积系统中，随着轨道能隙变小，需要对MP2进行更大的校正。在S66集0.346 kcal/mol上，具有F12校正的限制分母MP2的均方根偏差（RD-MP2-F12）小于MP2-F12的一半。RD-MP2的相互作用能与一系列聚芳烃二聚体的色散校正密度泛函理论的相互作用能相似。然而，对于C60-富勒烯二聚体，RD-MP2-F12的结果有些偏离实验估计，表明该系统需要明确包含高阶相关。
A new one-parameter correction scheme to second-order Møller–Plesset many-body perturbation theory (MP2) has been proposed to correctly evaluate intermolecular interaction energies of large π–π dispersion interaction systems as well as hydrogen-bonded and σ–σ dispersion interaction ones. The scheme restrains the denominator of the MP2 correlation energy expression based on the observation that larger corrections to MP2 are required as the orbital energy gaps become small as in large π–π stacking systems. The root-mean-square-deviation of the restrained denominator MP2 with F12 correction (RD-MP2-F12) on the S66 set of 0.346 kcal/mol is less than half of that of MP2-F12. The interaction energies of RD-MP2 are similar to those of dispersion corrected density functional theory for a series of polyaromatic hydrocarbon dimers. For the C60-fullerene dimer, however, the RD-MP2-F12 result somewhat deviates from the experimental estimate, indicating that an explicit inclusion of higher order correlation is required for the system.