Adiabatic potential-energy curves of long-range Rydberg molecules: Two-electronR-matrix approach

Abstract

We introduce a computational method developed for study of long-range molecular Rydberg states of such systems that can be approximated by two electrons in a model potential of the atomic cores. Only diatomic molecules are considered. The method is based on a two-electron Rmatrix approach inside a sphere centered on one of the atoms. The wave function is then connected to a Coulomb region outside the sphere via multichannel version of the Coulomb Green's function.This approach is put into a test by its application to a study of Rydberg states of the hydrogen molecule for internuclear distances R from 20 to 400 bohrs and energies corresponding to n from 3 to 22. The results are compared with previous quantum chemical calculations (lower quantum numbers n) and computations based on contact potential models (higher quantum numbers n).

Observation of spin-orbit-dependent electron scattering using long-range Rydberg molecules

“…Precision spectroscopy data will therefore spark increased efforts, e.g. in the development of appropriate R-matrix methods [44] or the inclusion of spin interactions in Green's function approaches, to obtain a consistent theoretical treatment.…”

Generalized local frame-transformation theory for ultralong-range Rydberg molecules

“…In the following, the GLFT approach is applied to the Rb * -Rb system to benchmark it against other state-of-the-art methods, namely, the diagonalization of Omont-Fermi pseudopotentials and the Coulomb Green's function method. The S-and P-wave phase shifts of the "electron-perturber" subsystem are obtained by a nonrelativistic two electron R-matrix method [47,48]. Recall that the S-and P-wave electronperturber phase shifts give rise to the trilobite and butterfly molecules, respectively.…”

Generalized local frame transformation theory for ultralong-range Rydberg molecules

“…In the following the GLFT approach is applied to the Rb * −Rb system to benchmark it against other state-of-the-art methods, namely the diagonalization of Omont/Fermi pseudopotentials and the Coulomb Green's function method. The S− and P −wave phase shifts of the "electron-perturber" subsystem are obtained by a non-relativistic two electron R-matrix method [47,48]. Recall that the S− and P −wave electronperturber phase shifts give rise to the trilobite and butterfly molecules, respectively.…”