Bound and resonance states of the dipolar anion of hydrogen cyanide: Competition between threshold effects and rotation in an open quantum system

Abstract

Bound and resonance states of the dipole-bound anion of hydrogen cyanide HCN$^-$ are studied using a non-adiabatic pseudopotential method and the Berggren expansion technique involving bound states, decaying resonant states, and non-resonant scattering continuum. We devise an algorithm to identify the resonant states in the complex energy plane. To characterize spatial distributions of electronic wave functions, we introduce the body-fixed density and use it to assign families of resonant states into collective rotational bands. We find that the non-adiabatic coupling of electronic motion to molecular rotation results in a transition from the strong-coupling to weak-coupling regime. In the strong coupling limit, the electron moving in a subthreshold, spatially extended halo state follows the rotational motion of the molecule. Above the ionization threshold, electron's motion in a resonance state becomes largely decoupled from molecular rotation. Widths of resonance-band members depend primarily on the electron orbital angular momentum.