Magnetic coupling between nuclear motion and nuclear spins in molecules

Abstract

Among the possible types of magnetic dipole interactions in molecular systems, couplings between nuclear motion and the nuclear spin have probably received the least attention in molecular spectroscopy. Although very small in comparison to effects related to electron spin, this type of hyperfine interaction plays an important role in the NMR spectroscopy of molecular systems. While measurement and prediction of spin-rotation tensors are a common place, vibrationally induced effects still lack a comprehensive description. In this article we develop a generic, theoretical framework that is well embedded in modern electronic structure theory and inspired by the Breit-Pauli Hamiltonian for electronic interactions, distinguishing between nuclear spin-orbit and spin-other-orbit contributions. We show that the interaction of nuclear spins with pseudorotational excitations of highly symmetric molecules may lead to experimentally accessible hyperfine splittings in NMR spectra, triggered by infrared light.

Author accepted version of the manuscript published in Molecular Physics. The SI is appended to the main manuscript; The previous version had a sign error in Equation (26), that effected numerical values in the tables and subsequent equations

References in corpus (7)

• Dynamical Multiferroicity
• Orbital magnetic moments of phonons
• Large effective magnetic fields from chiral phonons in rare-earth halides
• Phono-magnetic analogs to opto-magnetic effects
• Controlling the Rotational and Hyperfine State of Ultracold ${}^{87}$Rb${}^{133}$Cs Molecules
• Vibronic effects on the quantum tunnelling of magnetisation in Kramers single-molecule magnets
• Molecular Pseudorotation in Phthalocyanines as a Tool for Magnetic Field Control at the Nanoscale