Signatures of s-wave scattering in bound electronic states

Abstract

We compute EOM-EA-CCSD and EOM-EA-CCSDT potential energy curves and one-electron properties of several anions at bond lengths close to where these states become unbound. In the potential energy curves of the totally symmetric anions of HCl and pyrrole, which are associated with s-wave scattering states at the equilibrium bond lengths of the parent neutral molecules, we observe on inclusion of diffuse basis functions a pronounced bending effect near the crossing points with the potential energy curves of the neutral molecules. Additionally, we observe that the Dyson orbital and second moment of the electron density become extremely large in this region. In particular, the second moment of the HCl anion becomes 5 orders of magnitude times larger over a range of 5 pm. This behaviour is very different to the well-characterised non-totally symmetric anions of dinitrogen and dihydrogen that correspond to electronic resonances at the equilibrium bond lengths of their parent neutral molecules. Our work thus shows that bound state electronic-structure methods can distinguish between anions that turn into electronic resonances and those associated with s-wave scattering states.