Ultralong-Range Rydberg Molecules of Mercury: Extending the Frontier of Atomic and Molecular
Physics
Introduction
Atoms and molecules constitute the foundation of matter, with their behavior traditionally explained
through quantum mechanics and chemical bonding theory. While canonical molecules, such as H₂ or
CO₂, are governed by electron sharing or transfer, advances in ultracold physics have uncovered
unconventional binding mechanisms. Among the most striking examples are ultralong-range
Rydberg molecules, bound not by covalent or ionic interactions but through the scattering of a
Rydberg electron off a nearby ground-state atom.
The recent paper “Ultralong-range Rydberg molecules of Hg atoms” (Wojciechowska, Tomza, & Eiles,
2024) expands this field by investigating such exotic molecules in mercury (Hg). Unlike alkali atoms,
which have been extensively studied in Rydberg contexts, mercury is a heavy multivalent species
whose electron configuration introduces nontrivial spin–orbit and electron–electron coupling effects.
The work is a significant step toward broadening our understanding of ultralong-range molecular
physics beyond the alkali paradigm.
Rydberg Atoms and Molecules
A Rydberg atom is formed when an electron is excited to a very high principal quantum number (n).
The electron’s orbit becomes extremely large, sometimes spanning hundreds of nanometers, and the
atom acquires exaggerated properties such as high polarizability and sensitivity to external fields.
When such a Rydberg atom encounters another atom, the delocalized electron can scatter off the
neutral perturber, resulting in a weak but extended binding mechanism.
This leads to ultralong-range Rydberg molecules (ULRM) whose bond lengths far exceed those of
ordinary molecules. In some cases, the ground-state atom may even sit inside the electron’s orbital
path, producing unusual molecular geometries. ULRMs are valuable not only as quantum mechanical
curiosities but also as platforms for studying few-body physics, ultracold scattering, and potential
quantum information applications.
The Mercury Case
Most prior ULRM studies have focused on alkali atoms such as rubidium or cesium, which have a
single valence electron. Mercury, however, is a multivalent atom with complex electronic structure.
Its heavy nucleus also enhances relativistic spin–orbit coupling, making it a compelling candidate for
exploring new classes of molecular states.
The authors of the paper examine two classes of molecules:
1. Homonuclear Hg*Hg: a Rydberg-excited mercury atom interacting with a ground-state
mercury atom.
2. Heteronuclear Hg*Rb: a Rydberg mercury atom interacting with a ground-state rubidium
atom.
This dual approach highlights both the unique internal complexity of mercury and its interactions
with simpler alkali partners.
Methodology
The research employs quantum scattering theory and quantum defect models to calculate the
potential energy curves (PECs) of the proposed molecules. These PECs describe the dependence of
molecular energy on interatomic separation, thereby identifying possible bound states.
Special attention is paid to spin-dependent interactions, since mercury’s multivalency introduces
coupling between different electronic angular momentum channels. This requires a more elaborate
theoretical treatment than that used for alkali ULRMs.
