Accurate data on electric-dipole transition matrix elements (EDTMs) for bound-bound Rydberg-atom transitions have become increasingly important in science and technology. Here we compute radial EDTMs of rubidium in length, velocity, and acceleration forms for electric-dipole-allowed transitions between states with principal and angular-momentum quantum numbers $n$ and $\ell$ ranging from 15 to 100. Wave functions are computed based upon model potentials from [Phys. Rev. A 49, 982 (1994)]. Length-gauge EDTMs of strong low-$\ell$ Rydberg transitions, often employed in research and technology, are found to deviate from the fundamentally more accurate velocity-gauge form by approximately-$n$-independent and series-dependent shifts. The shift amount peaks at about $0.34e{a}_0$ for the Rb $nD\leftrightarrow (n+1)P$ series, a particularly strong Rydberg-transition series in Rb. The shift corresponds to relative EDTM corrections of up to $\approx {10}^{-3}$, which can be of concern in high-precision applications. We discuss the physical reasons for the observed gauge differences, explain the conditions for applicability of the velocity- and length-gauge forms for different transition series, and present a decision tree of how to choose EDTMs.

• Received 21 October 2021
• Accepted 23 December 2021

DOI:https://doi.org/10.1103/PhysRevA.105.012825