Wednesday, June 27, 2018

Eigenstate versus Zeeman-based approaches to the solid effect #DNPNMR

Rodríguez‐Arias, Inés, Alberto Rosso, and Andrea De Luca. “Eigenstate versus Zeeman-Based Approaches to the Solid Effect.” Magnetic Resonance in Chemistry 0, no. 0 (2017).

The solid effect is one of the simplest and most effective mechanisms for dynamic nuclear polarization. It involves the exchange of polarization between one electron and one nuclear spin coupled via the hyperfine interaction. Even for such a small spin system, the theoretical understanding is complicated by the contact with the lattice and the microwave irradiation. Both being weak, they can be treated within perturbation theory. In this work, we analyze the two most popular perturbation schemes: the Zeeman and the eigenstate-based approaches, which differ in the way the hyperfine interaction is treated. For both schemes, we derive from first principles an effective Liouville equation that describes the density matrix of the spin system; we then study numerically the behavior of the nuclear polarization for several values of the hyperfine coupling. In general, we obtain that the Zeeman-based approach underestimates the value of the nuclear polarization. By performing a projection onto the diagonal part of the spin-system density matrix, we are able to understand the origin of the discrepancy, which is due to the presence of parasite leakage transitions appearing whenever the Zeeman basis is employed.