A unique approach to address avoided crossings in the charge stabilization curve for LUMO identification.

Abstract

In quantum chemistry, Lowest Unoccupied Molecular Orbital (LUMO) is important for studying various chemical processes, including photochemical reactions, electron attached states, and electron excites states. Recently, an effective method has been introduced that involves the use of the Parametric Equation of Motion (PEM) in conjunction with the nuclear charge stabilization method for precise identification of true LUMO. However, the inclusion of extra diffuse functions in the basis set, which is necessary for describing electron-attached and electron-excited states, can cause issues due to the presence of the same symmetry states, leading to avoided crossing. Identifying the true LUMO among these avoided crossings is challenging due to the mixing of states and the exchange of their orbital character. This article introduces a modification of the PEM to identify the true LUMO by preventing the stabilization of specific states involved in avoided crossings. The present method is highly effective and requires minimal computational cost.