Assessment of the Second-Order Statically Screened Exchange Correction to the Random Phase Approximation for Correlation Energies.

Abstract

With increasing interelectronic distance, the screening of the electron–electron interaction by the presence of other electrons becomes the dominant source of electron correlation. This effect is described by the random phase approximation (RPA) which is therefore a promising method for the calculation of weak interactions. The success of the RPA relies on the cancellation of errors, which can be traced back to the violation of the crossing symmetry of the 4-point vertex, leading to strongly overestimated total correlation energies. By the addition of second-order screened exchange (SOSEX) to the correlation energy, this issue is substantially reduced. In the adiabatic connection (AC) SOSEX formalism, one of the two electron–electron interaction lines in the second-order exchange term is dynamically screened (SOSEX(W, vc)). A related SOSEX expression in which both electron–electron interaction lines are statically screened (SOSEX(W(0), W(0))) is obtained from the G3W2 contribution to the electronic self-energy. In contrast to SOSEX(W, vc), the evaluation of this correlation energy expression does not require an expensive numerical frequency integration and is therefore advantageous from a computational perspective. We compare the accuracy of the statically screened variant to RPA and RPA+SOSEX(W, vc) for a wide range of chemical reactions. While both methods fail for barrier heights, SOSEX(W(0), W(0)) agrees very well with SOSEX(W, vc) for charged excitations and noncovalent interactions where they lead to major improvements over RPA.