Atom-centered electric multipole moments can be extremely useful in chemistry, as they enable the systematic mapping of a complex electrostatic problem to a simpler model. However, since they do not correspond to physical observables, there is no unique way to define them. In this study, we present an extension of the dynamically generated RESP charges (D-RESP) method, referred to as xDRESP, where atom-centered multipoles are computed from mixed quantum mechanics/molecular mechanics molecular dynamics simulations. We compare the ability of xDRESP charges to reproduce the electrostatic potential, as well as molecular multipoles, against the performance of fixed point-charge models commonly used in force fields. Moreover, we highlight cases where xDRESP atomic multipoles can provide valuable information about chemical systems, such as indicating when polarization plays a significant role, and chemical reactions in which xDRESP atomic multipoles can be used as an on-the-fly analysis tool to track changes in electron density.