Stretching and bending dynamics in triatomic ultralong-range Rydberg molecules

Abstract

We investigate polyatomic ultralong-range Rydberg molecules consisting of three ground state atoms bound to a Rydberg atom via $s$- and $p$-wave interactions. By employing the finite basis set representation of the unperturbed Rydberg electron Green's function we reduce the computational effort to solve the electronic problem substantially. This method is subsequently applied to determine the potential energy surfaces of triatomic systems in electronic $s$- and $p$-Rydberg states. Their molecular geometry and resulting vibrational structure are analyzed within an adiabatic approach that separates the vibrational bending and stretching dynamics. This procedure yields information on the radial and angular arrangement of the nuclei and indicates in particular that kinetic couplings between bending and stretching modes induce a linear structure in triatomic $l=0$ ultralong-range Rydberg molecules.