A New Strategy to Optimize Complex Absorbing Potentials for the Computation of Resonance Energies and Widths.

Abstract

Complex absorbing potentials (CAPs) are artificial potentials added to electronic Hamiltonians to make the wave function of metastable electronic states square-integrable. This makes the electronic-structure theory of resonances comparable to that of bound states, thus reducing the complexity of the problem. However, the most often used box and Voronoi CAPs depend on several parameters that have a substantial impact on the numerical results. Among these parameters are the CAP strength and a set of spatial parameters that define the onset of the CAP. It has been a common practice to minimize the perturbation of the resonance states due to the CAP by optimizing the strength parameter while fixing the onset parameters, although the performance of this approach strongly depends on the chosen onset. Here, we introduce a more general approach that allows one to optimize not only the CAP strength but also the spatial parameters. We show that fixing the CAP strength and optimizing the spatial parameters is a reliable way to minimize CAP perturbations. We illustrate the performance of this new approach by computing resonance energies and widths of the temporary anions of dinitrogen, ethylene, and formic acid. This is done at the Hartree-Fock and equation-of-motion coupled-cluster singles and doubles levels of theory using full and projected box and Voronoi CAPs.