Second-order state-specific multireference Møller Plesset perturbation theory: Application to energy surfaces of diimide, ethylene, butadiene, and cyclobutadiene

Abstract

The complete active space spin-free state-specific multireference Møller-Plesset perturbation theory (SS-MRMPPT) based on the Rayleigh-Schrödinger expansion has proved to be very successful in describing electronic states of model and real molecular systems with predictive accuracy. The SS-MRMPPT method (which deals with one state while using a multiconfigurational reference wave function) is designed to avoid intruder effects along with a balanced description of both dynamic and static correlations in a size-extensive manner, which allows us to produce accurate potential energy surfaces (PESs) with a correct shape in bond-breaking processes. The SS-MRMPPT method is size consistent when localized orbitals on each fragment are used. The intruder state(s) almost inevitably interfere when computing the PESs involving the breaking of genuine chemical bonds. In such situations, the traditional effective Hamiltonian formalism often goes down, so that no physically acceptable solution can be obtained. In this work, we continue our analysis of the SS-MRMPPT method for systems and phenomena that cannot be described either with the conventional single-reference approach or effective Hamiltonian-based traditional MR methods. In this article, we investigate whether the encouraging results we have obtained at the SS-MRMPPT level in the study of cis-trans isomerization of diimide (N2H2), ethylene (C2H4), and 1,3-butadiene (C4H6) carry over to the study of chemical reactions. The energy surfaces of the double-bond flipping interconversion of the two equivalent ground and two lowest singlet state structures of cyclobutadiene have also been studied. All results have been discussed and assessed by comparing with other state-of-the-art calculations and corresponding experimental data whenever available