三阶Møller-Plesset微扰理论有用吗？轨道和标度的选择大大提高了热化学、动力学和分子间相互作用的准确性
Third-Order Møller-Plesset Perturbation Theory Made Useful? Choice of Orbitals and Scaling Greatly Improves Accuracy for Thermochemistry, Kinetics and Intermolecular Interactions
摘要：
我们开发和测试的方法，包括二阶和三阶微扰理论（MP3）使用从正则轨道优化的二阶微扰理论，$κ$ -OOMP 2，表示为MP3：$κ$-OOMP 2获得的轨道。测试MP3：$κ$ -OOMP 2显示，在7个数据集上，RMS误差比MP3小1.7至5倍。为了做得更好，在这些数据集之一上对二阶和三阶相关能量的缩放因子和正则化参数进行经验训练，得到表示为MP2.8的未正则化缩放（$c_2=1.0$ ; $c_3=0.8$）：$κ$ -OOMP 2。MP2.8：$κ$ -OOMP 2在热化学、动力学和非共价相互作用的6个测试数据集中的4个中产生了相对于MP3：$κ$ -OOMP 2的显著额外改进。值得注意的是，这两种方法在所考虑的7个数据集中的5个中优于具有单和双的耦合聚类，并且成本大大降低（没有$\mathcal{O}(N^6)$迭代）。
英文摘要：
We develop and test methods that include second and third-order perturbation theory (MP3) using orbitals obtained from regularized orbital-optimized second-order perturbation theory, $κ$-OOMP2, denoted as MP3:$κ$-OOMP2. Testing MP3:$κ$-OOMP2 shows RMS errors that are 1.7 to 5 times smaller than MP3 across 7 data sets. To do still better, empirical training of the scaling factors for the second- and third-order correlation energies and the regularization parameter on one of those data sets led to an unregularized scaled ($c_2=1.0$; $c_3=0.8$) denoted as MP2.8:$κ$-OOMP2. MP2.8:$κ$-OOMP2 yields significant additional improvement over MP3:$κ$-OOMP2 in 4 of 6 test data sets on thermochemistry, kinetics, and noncovalent interactions. Remarkably, these two methods outperform coupled cluster with singles and doubles in 5 of the 7 data sets considered, at greatly reduced cost (no $\mathcal{O}(N^6)$ iterations).
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