Theory of electronic resonances: Fundamental aspects and recent advances

Abstract

Electronic resonances are states that are unstable towards loss of electrons. They play critical roles in high-energy environments across chemistry, physics, and biology but are also relevant to processes under ambient conditions that involve unbound electrons. This feature article focuses on complex-variable techniques such as complex scaling and complex absorbing potentials that afford a treatment of electronic resonances in terms of discrete square-integrable eigenstates of non-Hermitian Hamiltonians with complex energy. Fundamental aspects of these techniques as well their integration into molecular electronic-structure theory are discussed and an overview of some recent developments is given: analytic gradient theory for electronic resonances, the application of rank-reduction techniques and quantum embedding to them, as well as approaches for evaluating partial decay widths.