Interatomic potentials, electric properties, and spectroscopy of the ground and excited states of the Rb_2 molecule: Ab initio calculations and effect of a non-resonant field

TL;DR

This paper develops a theoretical framework and performs ab initio calculations to understand how non-resonant laser fields influence the rovibrational and spectroscopic properties of the Rb₂ molecule, including its electronic states and transition behaviors.

Contribution

It introduces a comprehensive ab initio approach to model Rb₂ in non-resonant fields, incorporating spin-orbit and non-adiabatic effects, and explores field-induced control of molecular states.

Findings

Non-resonant fields hybridize rovibrational levels.

Spin-orbit and field interactions become comparable at high intensities.

Field control can modify the singlet-triplet character of levels.

Abstract

We formulate the theory for a diatomic molecule in a spatially degenerate electronic state interacting with a non-resonant laser field and investigate its rovibrational structure in the presence of the field. We report on \textit{ab initio} calculations employing the double electron attachment intermediate Hamiltonian Fock space coupled cluster method restricted to single and double excitations for all electronic states of the Rb$_2$ molecule up to $5s+5d$ dissociation limit of about 26.000$\,$cm$^{-1}$. In order to correctly predict the spectroscopic behavior of Rb$_2$, we have also calculated the electric transition dipole moments, non-adiabatic coupling and spin-orbit coupling matrix elements, and static dipole polarizabilities, using the multireference configuration interaction method. When a molecule is exposed to strong non-resonant light, its rovibrational levels get hybridized. We study the spectroscopic signatures of this effect for transitions between the X$^1\Sigma_g^+$ electronic ground state and the A$^1\Sigma_u^+$ and b$^3\Pi_u$ excited state manifold. The latter is characterized by strong perturbations due to the spin-orbit interaction. We find that for non-resonant field strengths of the order $10^9$W/cm$^2$, the spin-orbit interaction and coupling to the non-resonant field become comparable. The non-resonant field can then be used to control the singlet-triplet character of a rovibrational level.