Use of Parametric Equations of Motion to Study Metastable States

Abstract

In this thesis, a “resonance'' describes an electronically metastable state, that is, a state of a metastable anion that lies energetically above the ground state of the associated neutral molecule. These metastable states can decay by losing an electron, a process known as autodetachment, or by fragmenting into a stable anion and a radical, which is called dissociative electron attachment (DEA). In studying these metastable states, it is crucial to identify the Lowest Unoccupied Molecular Orbital (LUMO), as this is the orbital that will be filled by an electron. In this context, we have developed a methodology that utilizes the Parametric Equations of Motion (PEM) with the nuclear charge stabilization method to identify the LUMO obtained from the Self-Consistent-Field (SCF) solution. This approach demonstrates stability across different basis sets, including those with diffuse functions.