Molecular applications of state-specific multireference perturbation theory to HF, H2O, H2S, C2, and N2 molecules

Abstract

In view of the initial success of the complete active space (CAS) based size-extensive state-specific multireference perturbation theory (SS-MRPT) [J. Phys. Chem. A 103, 1822 (1999)] for relatively diverse yet simple chemically interesting systems, in this paper, we present the computation of the potential energy curves (PEC) of systems with arbitrary complexity and generality such as HF, H2O, H2S, C2, and N2 molecules. The ground states of such systems (and also low-lying singlet excited states of C2) possess multireference character making the description of the state difficult with single-reference (SR) methods. In this paper, we have considered the Møller–Plesset (MP) partitioning scheme [SS-MRPT(MP)] method. The accuracy of energies generated via SS-MRPT(MP) method is tested through comparison with other available results. Comparison with FCI has also been provided wherever available. The accuracy of this method is also demonstrated through the calculations of NPE (nonparallelism error) and the computation of the spectroscopic constants of all the above mentioned systems. The quality of the computed spectroscopic constants is established through comparison with the corresponding experimental and FCI results. Our numerical investigations demonstrate that the SS-MRPT(MP) approach provides a balanced treatment of dynamical and non-dynamical correlations across the entire PECs of the systems considered