Solid-State NMR Dipolar Recoupling in Presence of Large Chemical Shielding Anisotropies by Quaternion-Based Effective Hamiltonian Optimal Control

Abstract

Dipolar recoupling is a key element in magic-angle-spinning (MAS) solid-state NMR spectroscopy with reintroduced dipole-dipole coupling interactions providing information about internuclear distances and enabling transfer of polarization between spins in resolution-enhancing multiple-dimensional experiments. Such methods may be challenged in many important applications by the presence of large anisotropic nuclear spin interactions such as chemical shielding anisotropy. In this paper, we address this challenge by presenting quaternion-based optimal control. This is founded in single-spin operations enabling optimization of effective Hamiltonians with reduced influences from anisotropic shielding. Along with the principles underlying such optimizations, we present numerical and experimental demonstration of 19F to 13C polarization transfer in presence of 19F chemical shielding anisotropy.