State-specific multireference perturbation theory with improved virtual orbitals: Taming the ground state of F2, Be2, and N2

Abstract

Adaptation of improved virtual orbitals (IVOs) in state‐specific multireference perturbation theory using Møller–Plesset multipartitioning of the Hamiltonian (IVO‐SSMRPT) is examined in which the IVO‐complete active space configuration interaction (CASCI) is used as an inexpensive alternative to the more involved CAS‐self‐consistent field (CASSCF) orbitals. Unlike the CASSCF approach, IVO‐CASCI does not bear tedious and costly iterations beyond those in the initial SCF calculation. The IVO‐SSMRPT is intruder‐free, and explicitly size‐extensive. In the present preliminary study, the IVO‐SSMRPT method which relies on a small reference space is applied to study potential energy surfaces (PES) of the ground state of challenging, multiconfigurational F2, Be2, and N2 molecules. These systems provide a serious challenge to any ab initio methodology due to the presence of an intricate interplay of nondynamical and dynamical correlations to the entire PES. The quality of the computed PES has been judged by extracting spectroscopic parameters and vibrational levels. The reported results illustrate that the IVO‐SSMRPT method has a potential to yield accuracies as good as the CASSCF‐SSMRPT one with reduced computational labor. Even with small reference spaces, our estimates demonstrate a good agreement with the available experimental values, and some benchmark computations. The blend of accuracy and low computational cost of IVO‐SSMRPT should deserve future attention for the accurate treatment of electronic states of small to large molecular systems for which the wavefunction is characterized by various configurations.