Motional narrowing of spin relaxation in 2D perovskites by correlated exciton fluctuations

Two-dimensional organic-inorganic hybrid perovskite (2D-OIHP) quantum wells exhibit a triplet of bright exciton fine structure states near the band edge, enabling the generation of transient macroscopic spin alignments with circularly polarized light. Here, we investigate the microscopic origin of photoinduced spin relaxation in 2D-OIHPs using multidimensional coherent spectroscopy together with a theoretical framework that combines time-dependent perturbation theory with the Fokker-Planck equation. Analysis of the spectral line shapes reveals highly correlated exciton fluctuations within the fine structure manifolds of a pair of 2D-OIHPs featuring different organic layer thicknesses and polaron binding energies. In particular, the Gaussian correlation coefficients determined for the two lead-iodide-based systems range from 0.67 to 0.80, while their polaron binding energies span 11.8-18.9 meV. Incorporating time-coincident solvation dynamics into a stochastic model shows that these energy level correlations reduce the exciton-bath couplings and extend dephasing times for spin-flip transitions, even in spectral broadening regimes governed by Marcus-like kinetics (which are typically considered incompatible with motional narrowing). Since photoexcitation occurs on the seam of intersection between the excited-state free energy surfaces, spin relaxation can proceed without an activation barrier, provided it outpaces energy dissipation into the environment. Overall, these results demonstrate that correlated exciton fluctuations play a central role in accelerating spin depolarization in 2D-OIHPs through motional narrowing of coherences between exciton states.