The interaction between a Rydberg electron and a neutral atom situated inside its extended orbit is described via contact interactions for each atom-electron scattering channel. In ultracold environments, these interactions lead to long-range molecules with binding energies typically ranging from 10 to $1\times {10}^4$ MHz. These energies are comparable to the relativistic and hyperfine structure of the separate atomic components. Studies of molecular formation aiming to reproduce observations with spectroscopic accuracy must therefore include the hyperfine splitting of the neutral atom and the spin-orbit splittings of both the Rydberg atom and the electron-atom interaction. Adiabatic potential energy curves and permanent electric dipole moments are presented for ${\mathrm{Rb}}_2$ and ${\mathrm{Cs}}_2$. The influence of spin degrees of freedom on the potential energy curves and multipole moments probed in recent experimental work is elucidated, and the observed dipole moments of butterfly molecules are explained by the generalized ${}^{3}P_J$ pseudopotential derived here.

This PhD tutorial discusses ultra-long-range Rydberg molecules, the exotic bound states of a Rydberg atom and one or more ground state atoms immersed in the Rydberg electron’s wave function. This novel chemical bond is distinct from an ionic or covalent bond, and is accomplished by a very different mechanism: the Rydberg electron, elastically scattering off of the ground state atoms, exerts a weak attractive force sufficient to form the molecule in long-range oscillatory potential wells. In the last decade this topic has burgeoned into a vibrant and mature subfield of atomic and molecular physics following the rapidly developing capability of experiment to observe and manipulate these molecules. This tutorial focuses on three areas where this experimental progress has demanded more sophisticated theoretical descriptions: the structure of polyatomic molecules, the influence of electronic and nuclear spin, and the behavior of these molecules in external fields. The main results are a collection of potential energy curves and electronic wave functions which together describe the physics of Rydberg molecules. Additionally, to facilitate future progress in this field, this tutorial provides a general overview of the current state of experiment and theory.

Sufficiently high densities in Bose–Einstein condensates provide favorable conditions for the production of ultralong-range polyatomic molecules consisting of one Rydberg atom and a number of neutral ground state atoms. The chemical binding properties and electronic wave functions of these exotic molecules are investigated analytically via hybridized diatomic states. The effects of the molecular geometry on the system’s properties are studied through comparisons of the adiabatic potential curves and electronic structures for both symmetric and randomly configured molecular geometries. General properties of these molecules with increasing numbers of constituent atoms and in different geometries are presented. These polyatomic states have spectral signatures that lead to non-Lorentzian line-profiles.

We observe a series of conical intersections in the potential energy curves governing both the collision between a Rydberg atom and a ground-state atom and the structure of Rydberg molecules. By employing the electronic energy of the Rydberg atom as a synthetic dimension we circumvent the von Neumann–Wigner theorem. These conical intersections can occur when the Rydberg atom’s quantum defect is similar in size to the electron–ground-state atom scattering phase shift divided by $\pi$, a condition satisfied in several commonly studied atomic species. The conical intersections have an observable consequence in the rate of ultracold $l$-changing collisions of the type $\mathrm{Rb}(nf)+\mathrm{Rb}(5s)\to \mathrm{Rb}(nl>3)+\mathrm{Rb}(5s)$. In the vicinity of a conical intersection, this rate is strongly suppressed, and the Rydberg atom becomes nearly transparent to the ground-state atom.

A generalized class of ultralong-range Rydberg molecules is predicted which consist of a multichannel Rydberg atom whose outermost electron creates a chemical bond with a distant ground state atom. Such multichannel Rydberg molecules exhibit favorable properties for laser excitation, because states exist where the quantum defect varies strongly with the principal quantum number. The resulting occurrence of near degeneracies with states of high orbital angular momentum promotes the admixture of low $l$ into the high $l$ deeply bound “trilobite” molecule states, thereby circumventing the usual difficulty posed by electric dipole selection rules. Such states also can exhibit multiscale binding possibilities that could present novel options for quantum manipulation.

The quantum electrodynamical (QED) process of Compton scattering in strong magnetic fields is commonly invoked in atmospheric and inner magnetospheric models of x-ray and soft gamma-ray emission in high-field pulsars and magnetars. A major influence of the field is to introduce resonances at the cyclotron frequency and its harmonics, where the incoming photon accesses thresholds for the creation of virtual electrons or positrons in intermediate states with excited Landau levels. At these resonances, the effective cross section typically exceeds the classical Thomson value by over 2 orders of magnitude. Near and above the quantum critical magnetic field of 44.13 TeraGauss, relativistic corrections must be incorporated when computing this cross section. This profound enhancement underpins the anticipation that resonant Compton scattering is a very efficient process in the environs of highly magnetized neutron stars. This paper presents formalism for the QED magnetic Compton differential cross section valid for both subcritical and supercritical fields, yet restricted to scattered photons that are below pair creation threshold. Calculations are developed for the particular case of photons initially propagating along the field, and in the limit of zero vacuum dispersion, mathematically simple specializations that are germane to interactions involving relativistic electrons frequently found in neutron star magnetospheres. This exposition of relativistic, quantum, magnetic Compton cross sections treats electron spin dependence fully, since this is a critical feature for describing the finite decay lifetimes of the intermediate states. Such lifetimes are introduced to truncate the resonant cyclotronic divergences via standard Lorentz profiles. The formalism employs both the traditional Johnson and Lippmann (JL) wave functions and the Sokolov and Ternov (ST) electron eigenfunctions of the magnetic Dirac equation. The ST states are formally correct for self-consistently treating spin-dependent effects that are so important in the resonances. It is found that the values of the polarization-dependent differential cross section depend significantly on the choice of ST or JL eigenstates when in the fundamental resonance but not outside of it, a characteristic that is naturally expected. Relatively compact analytic forms for the cross sections are presented that will prove useful for astrophysical modelers.