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arXiv:2108.10475 · Physical Review A

Nonadiabatic decay of Rydberg-atom–ion molecules

Alisher Duspayev, Georg A. Raithel

Published Jan 14, 2022• 13 citations
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Abstract

The decay of Rydberg-atom--ion molecules (RAIMs) due to nonadiabatic couplings between electronic potential-energy surfaces is investigated. We employ the Born-Huang representation and perform numerical simulations using a Crank-Nicolson algorithm. The nonadiabatic lifetimes of rubidium RAIMs for the lowest ten vibrational states, $\ensuremath{\nu}$, are computed for selected Rydberg principal quantum numbers, $n$. The nonadiabatic lifetimes are found to generally exceed the radiative Rydberg-atom lifetimes. We observe and explain a trend of the lifetimes as a function of $\ensuremath{\nu}$ and $n$, and attribute irregularities to quantum interference arising from a shallow potential well in an inner potential surface. Our results will be useful for future spectroscopic studies of RAIMs.

DOI
10.1103/physreva.105.012810

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The decay of Rydberg-atom--ion molecules (RAIMs) due to nonadiabatic couplings between electronic potential-energy surfaces is investigated. We employ the Born-Huang representation and perform numerical simulations using a Crank-Nicolson algorithm. The nonadiabatic lifetimes of rubidium RAIMs for the lowest ten vibrational states, \ensuremathν\ensuremath{\nu}\ensuremathν, are computed for selected Rydberg principal quantum numbers, nnn. The nonadiabatic lifetimes are found to generally exceed the radiative Rydberg-atom lifetimes. We observe and explain a trend of the lifetimes as a function of \ensuremathν\ensuremath{\nu}\ensuremathν and nnn, and attribute irregularities to quantum interference arising from a shallow potential well in an inner potential surface. Our results will be useful for future spectroscopic studies of RAIMs.
Long-range Rydberg molecules are typically bound in wells formed in their oscillatory potential energy curves. In alkaline Rydberg molecules, bound vibrational states exist even when these potential wells are disrupted by level repulsion from the steep butterfly potential energy curve induced by a scattering shape resonance. The binding in this case is attributed to quantum reflection. However, the rapidly varying regions of the potential energy landscape where quantum reflection occurs often coincide with regions where nonadiabatic coupling becomes significant. By comparing the molecular states calculated within the Born-Oppenheimer approximation, where quantum reflection is the only binding mechanism, with those obtained from the full set of coupled channel equations, we assess the effects of nonadiabatic coupling on vibrational energies and lifetimes. Our findings show that these couplings can stabilize the molecule by providing an additional barrier which protects the vibrational states from predissociation and nonradiative transitions. There can also be extreme cases where nonadiabatic coupling completely dominates the binding and the molecular lifetimes saturate at the atomic Rydberg lifetime.
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We consider ultralong-range polyatomic Rydberg molecules formed by combining a Rydberg cesium atom and a ground-state RbCs molecule. We explore the regime where the charge-dipole interaction due to the Rydberg electron with the diatomic polar molecule couples the quantum defect Rydberg states Cs(ns)\mathrm{Cs}(ns)Cs(ns) to the nearest degenerate hydrogenic manifold. We consider polyatomic Rydberg molecules in states which are amenable to production in optical tweezers and study the influence of nonadiabatic coupling on the likelihood of their formation. The decay rates of the vibrational states reflect the interference signature of wave function spread in different coupled potential wells.
We investigate the non-adiabatic quantum dynamics of ultralong-range Rydberg molecules using a vibronically coupled two-channel treatment. The two-channels are composed of coupled trilobite and butterfly electronic states, formed as a result of SSS-wave and PPP-wave scattering of high angular momentum Rydberg electrons with perturbing ground state atoms. Within the Born-Oppenheimer treatment, the PPP-wave scattering channel introduces an adiabatic decay pathway that affects the stability and lifetimes of trilobite states. Our numerical results show that the vibronic coupling is dependent on the principal quantum number nnn, and for certain nnn there is non-adiabatic stabilization against internal molecular decay, facilitating previously studied dynamical effects in pure trilobite molecules. Apart from the internal diffraction effect caused by the backscattering of vibrational wavepackets from the trilobite potential, we also observe interesting multi-well tunneling effects during low-energy oscillations for a range of nnn-values. Our work serves to highlight that the unique vibrational coordinate dependent electronic structure of these polar molecules, along with high level densities, promise many exciting dynamical effects.
We investigate predissociation in homonuclear (87^{87}87Rb∗^*∗87^{87}87Rb+^++) and heteronuclear (87^{87}87Rb∗^*∗7^{7}7Li+^++) long-range Rydberg atom-ion molecules. Owing to their micron-scale bond lengths, these dissociate on time scales far removed from those of more tightly bound diatomic molecules. We employ the eigenchannel RRR-matrix method to compute predissociation rates for a broad range of principal quantum numbers nnn. The rates depend strongly on the mass, but more remarkably display a rapid and periodic variation as a function of nnn as well as within a single vibrational ladder. A semiclassical Landau-Zener-Stückelberg analysis reveals that Stückelberg interference governs the decay process and produces the observed variation in the molecular lifetime. Although the heavy mass of the homonuclear Rb molecule constrains its predissociation rates to a sub-kHz level, the lighter molecule 87^{87}87Rb∗^*∗7^{7}7Li+^++ dissociates on time scales competitive with radiative and collisional decay. This can enable in situ study of non-adiabatic decay via ion microscopy.
Ultralong-range Rydberg molecules provide an exciting testbed for molecular physics at exaggerated scales. In the so-called trilobite and butterfly Rydberg molecules, the Born-Oppenheimer approximation can fail due to strong nonadiabatic couplings arising from the combination of radial oscillations and rapid energy variations in the adiabatic potential energy curves. We utilize an accurate coupled-channel treatment of the vibronic system to observe the breakdown of Born-Oppenheimer physics, such as nonadiabatic trapping and decay of molecular states found near pronounced avoided crossings in the adiabatic potential curves. Even for vibrational states localized far away from avoided crossings, a single-channel model is quantitatively sufficient only after including the diagonal nonadiabatic corrections to the Born-Oppenheimer potentials. Our results indicate the importance of including nonadiabatic physics in the description of ultralong-range Rydberg molecules and in the interpretation of measured vibronic spectra.