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The practical utility of M{\o}ller-Plesset (MP) perturbation theory isseverely constrained by the use of Hartree-Fock (HF) orbitals. It has recentlybeen shown that use of regularized orbital-optimized MP2 orbitals and scalingof MP3 energy could lead to a significant reduction in MP3 error (J. Phys.Chem. Lett. 10, 4170, 2019). In this work we examine whether density functionaltheory (DFT) optimized orbitals can be similarly employed to improve theperformance of MP theory at both the MP2 and MP3 levels. We find that use ofDFT orbitals leads to significantly improved performance for prediction ofthermochemistry, barrier heights, non-covalent interactions, and dipole momentsrelative to standard HF based MP theory. Indeed MP3 (with or without scaling)with DFT orbitals is found to surpass the accuracy of coupled cluster singlesand doubles (CCSD) for several datasets. We also found that the results are notparticularly functional sensitive in most cases, (although range-separatedhybrid functionals with low delocalization error perform the best). MP3 basedon DFT orbitals thus appears to be an efficient, non-iterative $O(N^6)$ scalingwave function approach for single-reference electronic structure computations.Scaled MP2 with DFT orbitals is also found to be quite accurate in many cases,although modern double hybrid functionals are likely to be considerably moreaccurate.

Third order M{\o}ller-Plesset theory made more useful? The role of density functional theory orbitals