Polarization transfers are crucial building blocks in magnetic resonance experiments, i.e., they can be used to polarize insensitive nuclei and correlate nuclear spins in multidimensional nuclear magnetic resonance (NMR) spectroscopy. The polarization can be transferred either across different nuclear spin species or from electron spins to the relatively low-polarized nuclear spins. The former route occurring in solid-state NMR can be performed via cross polarization (CP), while the latter route is known as dynamic nuclear polarization (DNP). Despite having different operating conditions, we opinionate that both mechanisms are theoretically similar processes in ideal conditions, i.e., the electron is merely another spin-1/2 particle with a much higher gyromagnetic ratio. Here, we show that the CP and DNP processes can be described using a unified theory based on average Hamiltonian theory combined with fictitious operators. The intuitive and unified approach has allowed new insights into the cross-effect DNP mechanism, leading to better design of DNP polarizing agents and extending the applications beyond just hyperpolarization. We explore the possibility of exploiting theoretically predicted DNP transients for electron–nucleus distance measurements—such as routine dipolar-recoupling experiments in solid-state NMR.
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