State-specific complete active space multireference Møller–Plesset perturbation approach for multireference situations: illustrating the bond breaking in hydrogen halides

Abstract

Assessment of the complete active space-based state-specific multireference Møller–Plesset perturbation theory, SS-MRMPPT, has been performed on the ground states of HX (X = F, Cl, and Br) systems through the computation of potential energy surface (PES) and spectroscopic constants (such as equilibrium bond lengths, rotational constants, centrifugal distortion constants, vibrational frequencies, anharmonicity constants, and dissociation energies that are closely related to the shape and accuracy of the energy surfaces) extracted from the computed PES. The SS-MRMPPT (involves multiple amplitude sets to parametrize the exact wavefunction) approach isolates one of the several states provided by an effective Hamiltonian in an attempt to avert intruder states in size-extensive manner and hence it forms the basis of a robust approach to the electron correlation problem in cases where a multireference formalism is required. The absence of intruder problem makes SS-MRMPPT an interesting choice for the calculation of the dissociation energy surface(s). The performance of the method has been judged by comparing the results with calculations provided by current generation ab initio methods (multireference or single-reference methods) and we found, in general, a very good accordance between them which clearly demonstrates the usefulness of the SS-MRMPPT method.