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

P Giannakeas,Jan M Rost,F Robicheaux,Matthew T Eiles

doi:10.1103/physreva.102.033315

Abstract

A detailed theoretical framework for highly excited Rydberg molecules is developed based on the generalized local frame transformation. Our approach avoids the use of pseudopotentials and yields analytical expressions for the body-frame reaction matrix. The latter is used to obtain the molecular potential energy curves, but equally it can be employed for photodissociation, photoionization, or other processes. To illustrate the reliability and accuracy of our treatment we consider the Rb$^*-$Rb Rydberg molecule and compare our treatment with state-of-the-art alternative approaches. As a second application, the present formalism is used to re-analyze the vibrational spectra of Sr$^*-$Sr molecules, providing additional physical insight into their properties and a comparison of our results with corresponding measurements.

Highlights

Rydberg molecules constitute one of the most exotic physical systems in quantum chemistry
Theoretical studies showed that the delicate nature of the binding mechanism results in the formation of a class of weakly bound molecules with bond lengths of the order of a few hundred nanometers [1,2]. These ultralong-range Rydberg molecules (ULRMs) are subdivided into “trilobite” [1] and “butterfly” [2] molecular species originating from the Sand P-wave “electron-perturber” interactions
The state of the art of these molecules is reviewed in Refs. [8,9,10]

Summary

Introduction

Rydberg molecules constitute one of the most exotic physical systems in quantum chemistry. Theoretical studies showed that the delicate nature of the binding mechanism results in the formation of a class of weakly bound molecules with bond lengths of the order of a few hundred nanometers [1,2]. These ultralong-range Rydberg molecules (ULRMs) are subdivided into “trilobite” [1] and “butterfly” [2] molecular species originating from the Sand P-wave “electron-perturber” interactions. The state of the art of these molecules is reviewed in Refs. [8,9,10]

Methods

Results

Conclusion