Nugatory said:
There's no such thing as "in transit" and hence no such thing as "transiently free". The electron is never between one orbital and another, there are no "in-between" states.
This can be misleading, because the emission of a photon is a continuous process, described by unitary time evolution. However, in relativistic QFT it is not possible to give the transient state a proper meaning in terms of a particle interpretation. The only observable quantities are S-matrix elements, describing the transition probabilities from one asymptically free state to another.
Bremsstrahlung, as discussed here, is however a subtle issue, because there are IR and collinear divergences, which are, however, an artificial problem, originating from the fact that in theories, where massless particles are involved (here the photon), the usually used plane waves are not the true asymptotic free states. These are coherent states, which can be obtained in perturbation theory by appropriate soft-photon resummations.
E.g., in leading order of scattering of an electron on an external (Coulomb) potential, emitting one additional real photon, you need to take into account the next-to-leading order for elastic scattering, because you cannot distinguish physically the elastic scattering of the electron on the potential and the scattering plus the emission of the photon with an energy smaller than the energy resolution of your detectors. Look for the keywords "Bloch and Nordsieck" in any good book on QED. The scattering of an electron on a external Coulomb field is nicely discussed in Itzykson, Zuber, Quantum Field Theory.