REMP: A hybrid perturbation theory providing improved electronic wavefunctions and properties.

Abstract

We propose a new perturbation theoretical approach to the electron correlation energy by choosing the zeroth order Hamiltonian as a linear combination of the corresponding "Retaining the Excitation degree" (RE) and the Møller-Plesset (MP) operators. In order to fulfill Kato cusp conditions, the RE and MP contributions are chosen to sum up to one. 15% ± 5% MP contribution is deduced to be in an optimal range from a fit of the first order REMP wavefunction to near full configuration interaction reference data. For closed shell systems, the same range of MP weights shows best performance for equilibrium bond distances and vibrational wavenumbers of diatomic molecules, the reaction energies in the spin component scaled MP2 fit set, the transition energies of the BHPERI test set, and the parameterized coupled cluster with singles and doubles (pCCSD) fit set. For these properties, REMP outperforms all other tested perturbation theories at second order and shows equal performance as the best coupled pair approaches or pCCSD methods as well as the best double hybrid density functionals. Furthermore, REMP is shown to fulfill all required fundamental boundary conditions of proper wavefunction based quantum chemical methods (unitary invariance and size consistency).