title: Why does MP2 work?
abstract: We show analytically and numerically that the performance of second order Møller-Plesset (MP) perturbation theory (PT), coupled-cluster (CC) theory, and other perturbation theory approaches can be rationalized by analyzing the wavefunctions of these methods. While rather large deviations for the individual contributions of configurations to the electron correlation energy are found for MP wavefunctions, they profit from an advantageous and robust error cancellation: The absolute contribution to the correlation energy is generally underestimated for the critical excitations with small energy denominators and all other doubly excited configurations where the two excited electrons are coupled to a singlet. This is balanced by an overestimation of the contribution of triplet-coupled double excitations to the correlation energy. The even better performance of spin-component-scaled-MP2 theory is explained by a similar error compensation effect. The wavefunction analysis for the lowest singlet states of H2O, CH2, CO, and Cu+shows the predicted trends for MP methods, rapid but biased convergence of CC theory as well as the substantial potential of linearized CC, or retaining the excitation-degree (RE)-PT.
authors.affiliation: Institute of Physical and Theoretical Chemistry, University of Tübingen, 74076 Tübingen, Germany.
authors.forename: Reinhold F
authors.initials: RF
authors.lastname: Fink