DNP was first realized using the concept of the Overhauser effect, which is the perturbation of nuclear spin level populations observed in metals and free radicals when electron spin transitions are saturated by microwave irradiation. This effect relies on stochastic interactions between an electron and a nucleus. The "dynamic" initially meant to highlight the time-dependent and random interactions in this polarization transfer process.
The DNP phenomenon was theoretically predicted by Albert Overhauser in 1953
and initially drew some criticism from Norman Ramsey, Felix Bloch and other renowned physicists of the time on the grounds of being "thermodynamically improbable". The experimental confirmation by Carver and Slichter as well as an apologetic letter from Ramsey both reached Overhauser in the same year.
The so-called electron-nucleus cross-relaxation, which is responsible for the DNP phenomenon is caused by rotational and translational modulation of the electron-nucleus hyperfine coupling. The theory of this process is based essentially on the second-order time-dependent perturbation theory solution of the von Neumann equation for the spin density matrix.
While the Overhauser effect relies on time-dependent electron-nuclear interactions, the remaining polarizing mechanisms rely on time-independent electron-nuclear and electron-electron interactions.