Asymmetry in three-site relaxation exchange NMR.

The asymmetry of peak integrals in 2D relaxation maps of exchange between three sites indicates circular flow between the relaxation sites. This disagrees with the detailed balance according to which the exchange between any pair of sites must be balanced in terms of thermodynamic equilibrium. Confined diffusion of particles jumping randomly on a 2D checkerboard grid to any of their eight neighbor positions and confined gas diffusion were modeled in Monte Carlo simulations to explore the impact of topological constraints on particle exchange between three pools. Both models produce density variations across the pore and reveal that up to 1 % of the molecules move in circular paths between the relaxation pools. This motion is driven by different features of either algorithm. It is silent in terms of thermodynamic equilibrium, confirming that multi-site exchange maps are symmetric in this case. The coherent flux is argued to result from stochastic pore resonance related to diffusion eigenmodes. If it can be driven experimentally by external time-varying electric, magnetic, or ultrasonic fields, this may be a way to enhance heterogeneous catalysis.