Third-Order Møller-Plesset Perturbation Theory Made Useful? Choice of Orbitals and Scaling Greatly Improves Accuracy for Thermochemistry, Kinetics and Intermolecular Interactions

Abstract

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, $\kappa$-OOMP2, denoted as MP3:$\kappa$-OOMP2. Testing MP3:$\kappa$-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:$\kappa$-OOMP2. MP2.8:$\kappa$-OOMP2 yields significant additional improvement over MP3:$\kappa$-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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