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RYDBERG STATES AND RYDBERG MOLECULES

G. Herzberg

Published Jan 1, 1994• 0 citations
OpenAlex

Abstract

The history of Rydberg states in atoms and molecules will be briefly summarized. If the ground state of a molecular system is unstable (as for example two He atoms) while most excited states are stable Rydberg states, we may describe the system as a Rydberg molecule. The simplest diatomic example is the $He_{2}$ molecule, while the simplest polyatomic system would be the $H_{3}$ molecule discovered only in 1979. In recent years many other examples have been studied and will be briefly summarized.

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The history of Rydberg states in atoms and molecules will be briefly summarized. If the ground state of a molecular system is unstable (as for example two He atoms) while most excited states are stable Rydberg states, we may describe the system as a Rydberg molecule. The simplest diatomic example is the He2He_{2}He2​ molecule, while the simplest polyatomic system would be the H3H_{3}H3​ molecule discovered only in 1979. In recent years many other examples have been studied and will be briefly summarized.
Rydberg molecule, formed by one or more Rydberg atoms, exhibits remarkable properties, including an exceptionally large spatial extent, rich rovibrational level structures, permanent electric dipole moments, and a pronounced sensitivity to external fields. Based on the underlying binding mechanisms, Rydberg molecules can be divided into three categories, the ground-Rydberg molecule that is bound via a low-energy electron-atom scattering interaction between ground atom and Rydberg electron, the Rydberg-Rydberg molecule that is bound via a long-range electrostatic interaction between Rydberg atoms, and the ion-Rydberg molecule that is bound via single- or multi-polar interactions between Rydberg atom and ion. This review focuses on recent theoretical and experimental advances in diatomic Rydberg molecules, covering their formation and binding mechanisms, potential energy curves, experimental observations, and spectroscopic properties, with the aim of providing a comprehensive overview of the current state and future prospects of this rapidly developing field.
Controlling molecular binding at the level of single atoms is one of the holy grails of quantum chemistry. Rydberg macrodimers─bound states between highly excited Rydberg atoms─provide a novel perspective in this direction. Resulting from binding potentials formed by the strong, long-range interactions of Rydberg states, Rydberg macrodimers feature bond lengths in the micrometer regime, exceeding those of conventional molecules by orders of magnitude. Using single-atom control in quantum gas microscopes, the unique properties of these exotic states can be studied with unprecedented control, including the response to magnetic fields or the polarization of light in their photoassociation. The high accuracy achieved in spectroscopic studies of macrodimers makes them an ideal testbed to benchmark Rydberg interactions, with direct relevance to quantum computing and information protocols where these are employed. This review provides a historic overview and summarizes the recent findings in the field of Rydberg macrodimers. Furthermore, it presents new data on interactions between macrodimers, leading to a phenomenon analogous to Rydberg blockade at the level of molecules, opening the path toward studying many-body systems of ultralong-range Rydberg molecules.