Accurate and Efficient Spin–Phonon Coupling and Spin Dynamics Calculations for Molecular Solids

[Image: see text] Molecular materials are poised to play a significant role in the development of future optoelectronic and quantum technologies. A crucial aspect of these areas is the role of spin–phonon coupling and how it facilitates energy transfer processes such as intersystem crossing, quantum decoherence, and magnetic relaxation. Thus, it is of significant interest to be able to accurately calculate the molecular spin–phonon coupling and spin dynamics in the condensed phase. Here, we demonstrate the maturity of ab initio methods for calculating spin–phonon coupling by performing a case study on a single-molecule magnet and showing quantitative agreement with the experiment, allowing us to explore the underlying origins of its spin dynamics. This feat is achieved by leveraging our recent developments in analytic spin–phonon coupling calculations in conjunction with a new method for including the infinite electrostatic potential in the calculations. Furthermore, we make the first ab initio determination of phonon lifetimes and line widths for a molecular magnet to prove that the commonplace Born–Markov assumption for the spin dynamics is valid, but such “exact” phonon line widths are not essential to obtain accurate magnetic relaxation rates. Calculations using this approach are facilitated by the open-source packages we have developed, enabling cost-effective and accurate spin–phonon coupling calculations on molecular solids.