A scaled explicitly correlated F12 correction to second-order MOller-Plesset perturbation theory

摘要

An empirically scaled version of the explicitly correlated F12 correction to second-order MOller-Plesset perturbation theory (MP2-F12) is introduced. The scaling eliminates the need for many of the most costly terms of the F12 correction while reproducing the unscaled explicitly correlated F12 interaction energy correction to a high degree of accuracy. The method requires a single, basis set dependent scaling factor that is determined by fitting to a set of test molecules. We present factors for the cc-pVXZ-F12 (X = D, T, Q) basis set family obtained by minimizing interaction energies of the S66 set of small- to medium-sized molecular complexes and show that our new method can be applied to accurately describe a wide range of systems. Remarkably good explicitly correlated corrections to the interaction energy are obtained for the S22 and L7 test sets, with mean percentage errors for the double-zeta basis of 0.60% for the F12 correction to the interaction energy, 0.05% for the total electron correlation interaction energy, and 0.03% for the total interaction energy, respectively. Additionally, mean interaction energy errors introduced by our new approach are below 0.01 kcal mol(-1) for each test set and are thus negligible for second-order perturbation theory based methods. The efficiency of the new method compared to the unscaled F12 correction is shown for all considered systems, with distinct speedups for medium- to large-sized structures.