Iteration scheme for solving the system of coupled integro-differential equations for excited and ionized states of molecular systems (Q2633232)

Summary: Investigation of the interaction of electromagnetic radiation with molecular systems provides most of the information on their structure and properties. Interpretation of experimental data is directly determined by the knowledge of the structure of energy levels and its change in the transition of these systems to an excited state. A key task of the methods for calculating the molecular orbitals of excited states is to accurately describe the emerging vacancies of the molecular core, leading to radial relaxation of the electron density. We propose an iterative scheme for solving a system of coupled integro-differential equations for obtaining molecular orbitals of electron configurations with excited/ionized deep and subvalent shells in a single-center representation. The numerical procedure of the iterative scheme is reduced to solving a boundary value problem based on a combination of the three-point difference scheme of Numerov and Thomas algorithm. To increase the rate of convergence of the computational procedure, an accurate account is taken of the behavior of the electron density near the nuclei of the molecular system. The realization of the algorithm of the computational scheme is considered on the example of a diatomic hydrogen fluoride molecule. The energy characteristics of the ground and ionized states of the molecule are estimated, and also the spatial distribution of the electron density is presented for the example of the \(\sigma\)-symmetry shell.