The role of electronic excited states in the spin-lattice relaxation of spin-1/2 molecules.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39937899.
- Also identified by DOI 10.1126/sciadv.adr0168 and PMC identifier 11817928.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Magnetic resonance is a prime method for the study of chemical and biological structures and their dynamical processes. The interpretation of many of these experiments relies on understanding how the spin of unpaired electrons exchanges energy with their environment, or lattice, and relaxes to equilibrium. Here, we overcome the common use of effective spin Hamiltonians to describe spin-lattice relaxation in spin-1/2 and apply ab initio open quantum systems theory to their full molecular electronic wavefunction. Simulations for two Cr(V) coordination compounds under this framework show a marked improvement in accuracy and demonstrate that relaxation in spin-1/2 molecules is enabled by virtual transitions to molecular excited states with energy approaching 20,000 cm<sup>-1</sup>. This work establishes a connection between the original theory of Van Vleck and modern electronic structure methods, ultimately exemplifying the urgency of further advancing an ab initio approach to spin-lattice relaxation.