Weakly Bound Rydberg-Dipole Molecules

Dmitrii L. Dorofeev, B. A. Zon

Jianming Zhao, Jingxu Bai, Suying Bai +1 more

The ultralong-range Cs2 Rydberg molecules consisting of a Rydberg, nD5/2 ( principal quantum number n =35-38), and a ground state atom, 6S1/2 (F=4) are prepared by a two-photon photoassociation spectroscopy in an ultracold Cs gas. This kind of molecule is bound with the low energy scattering and has a permanent dipole moment. We observe two Rydberg-ground state molecular spectra, one is deep-bound molecule, TΣ state, bound by triplet s-wave scattering length and the other one is shallow-bound molecule, S,TΣ state, bound by mixed singlet-triplet s-wave scattering length. The binding energy of Rydberg-ground molecules are attained by analyzing the two photon photoassociation spectrum, corresponding permanent dipole moment is measured by applying an external electric field, which is compared to the calculation.

L. Suess

Low-energy electron transfer in collisions between a Rydberg atom and a target molecule can result in the formation of negative ions. Depending as to the properties of the target molecule the electron may be bound in a localized molecular orbital (valence-bound) or bound by its dipole potential in a diffuse orbital located at the positive end of the dipole (dipole-bound). Here we examine the properties of valence-bound and dipole-bound negative ions created through electron transfer in collision with Rydberg atoms, in particular, their lifetimes, collisional properties and electric-field-induced detachment characteristics. Intercomparison of the various data also leads to new insights into electron attachment to molecules that can support both valence-bound and dipole-bound negative ion states.

Robert S. Freund

Yi Liu

Electron transfer in collisions between atoms in high Rydberg states and polar targets can lead to the formation of dipole-bound negative ions in which the excess electron is weakly bound by the dipole potential of the neutral molecule. Their lifetimes and collisional destruction rates are studied using a Penning ion trap. Ion decay in the trap is characterized by a single exponential lifetime, ∼60 to 100 mus governed by BBR-induced photodetachment. The rate constants for destruction of these ions by rotational energy transfer in collisions with residual target gas present in the trap are large, ∼ 10-7cm3s-1. The dynamics of CH3CN- ion production through electron transfer are examined using velocity selected Rydberg atoms. The CH3CN- ion formation rate shows a strong velocity dependence and is relatively small, the associated rate constants being ∼ 0.5--1.0 x 10-8cm 3s-1. A curve-crossing model, which considers the effect of crossings between the diabatic potential curves for the covalent K(np)/CH3CN system and the ionic K+/CH 3CN- system is discussed and provides a clear explanation for the observations. Electron transfer in collisions between dipole-bound negative ions (CH 3CN- and C2H3CN-) and target gas, including attaching molecules like SF6 and polar molecules like CH3NO2, is examined using the Penning trap. A free-electron capture model is used to describe electron transfer to attaching molecules. A near-resonant charge transfer model is employed to describe collisions between dipole-bound anions and polar molecules. The rate constants predicted by these models are consistent with the experimental observations.

Hyunwook Park, Thomas F. Gallagher