The role of electronic excited states in the spin-lattice relaxation of spin-1/2 molecules

TL;DR

This paper reveals that in spin-1/2 molecules, electronic excited states and low-energy phonons significantly influence spin-lattice relaxation, challenging traditional models that focus only on low-energy spin interactions.

Contribution

It introduces an ab initio open quantum systems approach showing excited states and phonons dominate relaxation, providing a new framework for understanding spin dynamics.

Findings

Excited states above 20,000 cm$^{-1}$ drive relaxation.

Low-energy THz phonons contribute to thermalization.

Traditional low-energy spin interactions are less influential than previously thought.

Abstract

Magnetic resonance is a prime method for the study of chemical and biological structures and their dynamical processes. The interpretation of these experiments relies on considering the spin of electrons as the sole relevant degree of freedom. By applying ab inito open quantum systems theory to the full electronic wavefunction, here we show that contrary to this widespread framework the thermalization of the unpaired electron spin of two Cr(V) coordination compounds is driven by virtual transitions to excited states with energy higher than 20,000 cm$^{-1}$ instead of solely involving low-energy spin interactions such as Zeeman and hyperfine ones. Moreover, we found that a window of low-energy THz phonons contributes to thermalization, rather than a small number of high-energy vibrations. This work provides a drastic reinterpretation of relaxation in spin-1/2 systems and its chemical control strategies, and ultimately exemplifies the urgency of further advancing an ab initio approach to relaxometry.