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arXiv:2609.15644

Interactions and excitation blockade of Rydberg macrodimers

Dhiya Varghese, Rejish Nath, Simon Hollerith, Valentin Walther

Published Sep 14, 2026• 0 citations
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Abstract

We present a theoretical study of interactions between Rydberg macrodimers, molecular bound states of Rydberg atoms, and the largest known neutral homonuclear diatomic molecules. Accounting for the large number of molecular interaction channels from four interacting Rydberg atoms, we show that macrodimer-macrodimer interactions are anisotropic and similar in strength and range to atomic-state Rydberg interactions. Our analysis reveals the presence of two-atom, three-atom, and four-atom contributions in the bimolecular system, and elucidates how these interactions are rooted in the underlying atomic Rydberg-state couplings. Our calculations of the excitation blockade between macrodimers are in reasonable agreement with experimentally observed signals, and pave the way for the exploration of optically controlled collective quantum dynamics in molecular systems.

DOI
10.48550/arxiv.2609.15644

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We present a theoretical study of interactions between Rydberg macrodimers, molecular bound states of Rydberg atoms, and the largest known neutral homonuclear diatomic molecules. Accounting for the large number of molecular interaction channels from four interacting Rydberg atoms, we show that macrodimer-macrodimer interactions are anisotropic and similar in strength and range to atomic-state Rydberg interactions. Our analysis reveals the presence of two-atom, three-atom, and four-atom contributions in the bimolecular system, and elucidates how these interactions are rooted in the underlying atomic Rydberg-state couplings. Our calculations of the excitation blockade between macrodimers are in reasonable agreement with experimentally observed signals, and pave the way for the exploration of optically controlled collective quantum dynamics in molecular systems.
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.
We study long range interactions between two Rydberg atoms and predict the existence of ultralong range Rydberg dimers with equilibrium distances of many thousands of Bohr radii. We calculate the dispersion coefficients C5, C6, and C8 for two rubidium atoms in the same excited level np and find that they scale like n(8), n(11), and n(15), respectively. We show that for certain molecular symmetries these coefficients lead to long range potential wells that can support molecular bound levels. Such macrodimers would be very sensitive to their environment and could probe weak interactions. We suggest experiments to detect these macrodimers.
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In this thesis I present several theoretical methods to explore the excitation dynamics of Ultracold Rydberg systems in various regimes. For some applications the details of interactions between Rydberg atoms have to be carefully examined, while for others, the many-body aspect of Rydberg excitation may be crucial. In both cases, the basic prerequisite is to know the interactions sufficiently well. I will review the basic concepts how to evaluate molecular potentials in various Hund's cases and approximations. Long-range Rydberg-Rydberg interactions between Rydberg atoms induce ℓ-mixing which in certain situations gives rise to molecular resonances. For these resonances, we calculate long-range potentials in Hund's case (c) by diagonalization of an interaction matrix. The excitation dynamics of the resonances is always modeled as pair excitation. At high principal quantum number n, the interactions between Rydberg atoms can blockade the excitation of many surrounding atoms in the range of few μm. The atoms within this range are strongly correlated so that many-body treatments are, in general, needed. To describe this blockading effect and other manifestations of the collective behavior of Rydberg excitation, such as the many-body Rabi oscillations, spatial correlations between atoms and the fluctuations of the number of excited atoms, I have used three different approaches. In the mean-field approach the interactions between different atoms is modeled by a distribution of mean-field shifts for which a distribution of probabilities is calculated, A good agreement between the theoretical model and experimental measurements is found. To study the correlations between atoms the many-body wavefunction is numerically computed. The possibility of observing the many-body Rabi oscillations of Rydberg excitation and other aspects of many-body dynamics is analyzed. Although strong interactions cannot be treated perturbatively other expansions may be feasible. I will show that the expansion in powers of the single atom Rabi frequency can be evaluated in the interaction and Heisenberg picture. The expansion is expected to behave well for arbitrary strong interactions. ^
Systems of cold, interacting Rydberg atoms are of interest because they exhibit a wide range of collective quantum phenomena. This thesis describes experimental and theoretical work related to these systems with an emphasis on two phenomena: Rydberg excitation blockades and quantum-state-changing collisions. I begin by presenting a detailed calculation of the interaction energies of two Rydberg atoms for a variety of orientations, quantum states, and applied electric fields. The calculated energies are used to interpret the experimental results that follow. I then describe measurements showing that the widths of the distributions of Rydberg excitation number are related to the effectiveness of a Rydberg excitation blockade. These distributions are investigated as a function of principal quantum number, n, and applied electric field. In the presence of a Forster resonant field, sub-Poissonian distributions are measured. I next present a spectroscopic measurement of the energy level shift of a system of atoms which collectively shares two Rydberg excitations. The qualitative nature of the shift depends sensitively on the type of interactions between the atoms (van der Waals or dipole-dipole) and may be changed by changing the quantum state or applied electric field. This measurement provides the first spectroscopic proof that Rydberg excitation blockades are operative. Finally, I describe measurements of the probability for quantum state-changing and Penning-ionizing collisions to provide evidence for intrinsic, electric field-free-interaction resonances and complex many-body interactions in systems of cold Rydberg atoms.