Multifaceted Water Dynamics in Spherical Nanocages

M von Domaros and D Bratko and B Kirchner and G Hummer and A Luzar, JOURNAL OF PHYSICAL CHEMISTRY C, 123, 5989-5998 (2019).

DOI: 10.1021/acs.jpcc.8b11567

We present a new method to study position-dependent, anisotropic diffusion tensors inside spherically confined systems-a geometry that is common to many chemical nanoreactors. We use this method to elucidate the surprisingly rich solvent dynamics of confined water. The spatial variation of the strongly anisotropic diffusion predicted by the model agrees with the results of explicit molecular dynamics simulations. The same approach can be directly transferred to the transport of solutes to and from reaction sites located at nanoreactor interfaces. We complement our study by a detailed analysis of water hydrogen bond kinetics, which is intimately coupled to diffusion. Despite the inhomogeneity in structure and translational dynamics inside our nanocages, a single set of well-defined rate constants is sufficient to accurately describe the kinetics of hydrogen bond breaking and formation. We find that once system size effects have been eliminated, the residence times of water molecules inside the coordination shell of a hydrogen bond partner are well correlated to average diffusion constants obtained from the procedure above.

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