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International Reviews in Physical Chemistry

Collisions of Rydberg atoms with neutral targets

F. B. Dunning, Sitti Buathong

Published Apr 3, 2018• 5 citations
Publisher

Abstract

Atoms in highly excited Rydberg states possess physical characteristics quite unlike those associated with atoms in the ground or low-lying excited states. In particular, they are physically very large and are only very weakly bound. In consequence, collisions can lead to a wide variety of reaction processes many of which are unique to Rydberg species and have very large collision cross sections. In collisions with neutral targets, Rydberg atoms behave not as an atom but rather as a pair of well-separated independent scatterers, namely the core ion and the excited Rydberg electron. In the present article we discuss many of the different reactions that can occur when Rydberg atoms collide with neutral targets, focusing principally on reactions that are dominated by (binary) Rydberg electron-target interactions and include collisions with molecules that attach free low-energy electrons and with polar targets. In certain situations, however, interactions involving the Rydberg core ion are important. This is illustrated using as an example the destruction of ultralong-range Rydberg molecules excited in a cold dense gas.

DOI
10.1080/0144235x.2018.1512201

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Atoms in highly excited Rydberg states possess physical characteristics quite unlike those associated with atoms in the ground or low-lying excited states. In particular, they are physically very large and are only very weakly bound. In consequence, collisions can lead to a wide variety of reaction processes many of which are unique to Rydberg species and have very large collision cross sections. In collisions with neutral targets, Rydberg atoms behave not as an atom but rather as a pair of well-separated independent scatterers, namely the core ion and the excited Rydberg electron. In the present article we discuss many of the different reactions that can occur when Rydberg atoms collide with neutral targets, focusing principally on reactions that are dominated by (binary) Rydberg electron-target interactions and include collisions with molecules that attach free low-energy electrons and with polar targets. In certain situations, however, interactions involving the Rydberg core ion are important. This is illustrated using as an example the destruction of ultralong-range Rydberg molecules excited in a cold dense gas.
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We have theoretically studied the conditions of the behavior of a high Rydberg electron as a spectator to an ion-molecule reaction in high Rydberg neutral collisions. Adoption of a circular high Rydberg atom in the initial channel of the high Rydberg neutral collisions ensures the behavior of the high Rydberg electron as the spectator to interaction between an ion core of the high Rydberg atom and an incoming neutral species; i.e., the ion-molecule reaction. This theoretical consideration leads to equivalence between the high Rydberg neutral collision and the ion-molecule reaction with high accuracy. This equivalence gives us a possibility of probing the ion-molecule reaction at low energies without space-charge effects encountered in ion-beam experiments.
The mechanism of reactive processes in binary atomic encounters is investigated by employing a Rydberg atom as one of the reactants. This permits isolation of the excited valence electron so that its role in effecting the heavy-body process can be assessed. Penning ionization by a Rydberg atom, which is studied as an example of a reactive process, is shown to have a cross section significantly higher than might be inferred solely on the basis of overlap of the atomic wave functions of the ionic Rydberg core and the collision partner. A model to describe these reactive processes in which the nearly isolated Rydberg electron polarizes, and is therefore attracted by, the neutral ground-state reactant is proposed. This attraction occurs at an internuclear separation greater than that at which the ionic core of the Rydberg atom can substantially polarize the neutral atom but polarization of the neutral atom by the Rydberg electron leads to a transitory negative ion and concomitant Coulomb attraction to the ionic core. This Coulomb attraction thus leads to cross sections that are higher than would be calculated solely on the basis of atomic overlap.
Potassium atoms in selected high-lying Rydberg states (n <<< 1200) are used as a tool to probe threshold behavior in electron-molecule collisions. Collisions with non-polar electron attaching molecules such as CClsb4\\sb4sb4 are dominated by electron capture in a binary interaction between the Rydberg electron and target molecule allowing the study of electron attachment at electron energies of only a few mu\\mumueV. Analysis of the data shows the cross section for electron capture is consistent with the Wigner threshold law for an inelastic s-wave process. Collisions with polar molecules can lead to Rydberg atom destruction through transfer of molecular rotational energy to the Rydberg electron. Rydberg atom data obtained with polar targets are not consistent with scattering from a static dipole. However, the data are consistent with a threshold law that takes into account a rotationally-averaged induced dipole interaction that can possibly support bound or virtual states.
The large size and low binding energies, scaling as n 4 and n −2 , of Rydberg atoms make them nearly irresistible subjects for collision experiments. While one might expect collision cross sections to be enormous, by and large they are not. In fact, Rydberg atoms are quite transparent to most collision partners. Collisions involving Rydberg atoms can be broken into two general categories, collisions in which the collision partner, or perturber, interacts with the Rydberg atom as a whole, and those in which the perturber interacts separately with the ionic core and the Rydberg electron. The difference between these two categories is in essence a question of the range of the interaction between the perturber and the Rydberg atom relative to the size of the Rydberg atom. A few examples serve to clarify this point. A Rydberg atom interacting with a charged particle is a charge–dipole interaction with a 1/ R 2 interaction potential, and the resonant dipole–dipole interaction between two Rydberg atoms has a 1/ R 3 interaction potential. Here R is the internuclear separation of the Rydberg atom and the perturber. In both of these interactions the perturber interacts with the Rydberg atom as a whole. On the other hand when a Rydberg atom interacts with a N 2 molecule the longest range atom–molecule interaction is a dipole–induced dipole interaction with a potential varying as 1/ R 6 .
Processes involving a change of orbital angular momentum l and the dissociation of Rydberg molecules when they collide with inert-gas atoms are considered, using a method based on analyzing the terms of the interacting systems. The proposed method makes it possible to take into account the perturbations in a large group of Rydberg states that weakly penetrate into the ion core and to go beyond the limits of the two-level approximations [R. F. Stebbings and F. B. Dunning, eds., Rydberg States of Atoms and Molecules (Cambridge University Press, Cambridge, 1983; Mir, Moscow, 1985)] widely used in the theory of l mixing with the participation of Rydberg atoms. Using the Na**( nd )+Xe reaction as an example, it is demonstrated that this method gives good results in a wide range of variation of the principal quantum number n of the Rydberg electron ( n ≈10–40). Features of the l mixing and dissociation of Rydberg molecules are studied for the H 2 **+Xe system. It is shown that collisional dissociation occurs by the formation of an intermediate Rydberg state of the molecules, followed by self-decay into a dissociative continuum.