Second-order Møller–Plesset perturbation theory (MP2) approximates the exact Hartree–Fock (HF) adiabatic connection (AC) curve by a straight line. Thus, by using the deviation of the exact curve from the linear behavior, we construct an indicator for the accuracy of MP2. We then use an interpolation along the HF AC to transform the exact form of our indicator into a highly practical MP2 accuracy predictor (MAP) that comes at a negligible additional computational cost. We show that this indicator is already applicable to systems that dissociate into fragments with a nondegenerate ground state, and we illustrate its usefulness by applying it to the S22 and S66 datasets.
American Chemical Society
7 May 2020
Volume: 16 Issue: 7 Pages: 4141-4149
Journal of chemical theory and computation