Searching for the atomic scale mechanism of ice nucleating particles: hydration layer structures on K-Feldspar microcline surfaces from a combination of atomistic simulation and atomic force microscopy

Ice and mixed-phase clouds can form at moderate supercooling on seed particles through heterogeneous ice nucleation, but despite numerous experimental and computational investigations, understanding heterogeneous ice nucleation remains one of the great challenges in atmospheric science. While feldspar mineral dust particles have been identified as particularly good ice nucleating particles, they can exhibit different chemical composition and crystal structure, making it difficult to determine the atomistic details of the ice nucleation mechanism, both experimentally, and computationally. Here, we present systematic atomistic molecular dynamics studies of hydration layer structures at the interfaces of K-feldspar maximum microcline (001), (010), and (100) surfaces and water, at room temperature and moderate supercooling. Simulations on the fully hydroxylated α-terminated (001) cleavage plane reveal a complex lateral structure in the first water layer and a less ordered second layer. At room temperature, water exchange within the first hydration layer and between the first and second hydration layers occurs on a sub-nanosecond timescale. We also observe that surface potassium ions can go into solution and return to vacant surface sites on a timescale of tens of nanoseconds, but this causes surprisingly minor perturbations within the first hydration layer if the sampling time is sufficient. Hydration layer structures from simulation are in very good agreement with 3D atomic force microscopy data recently obtained for the first time on a freshly cleaved microcline surface in pure water (Dickbreder et al., 2024) – validating the accuracy of the atomistic model and providing an interpretation of the experimental data. However, the simulated hydration layer structures on the low energy (001) or (010) surfaces do not exhibit a lattice match with faces of cubic or hexagonal ice. Only the higher energy (100) surface with slightly strained lattice parameters can stabilize an ice interface at moderate supercooling in the simulations. Our results confirm previous findings (Kiselev et al., 2017; Soni and Patey, 2019) and indicate that the good ice nucleating properties of feldspars likely result from more complex active sites, possibly involving changes in surface chemistry, or topographic features such as defects, strained lattices, or step edges, which we are currently investigating.Dickbreder, T., Sabath, F., Reischl, B., Nilsson, R. V. E., Foster, A., Bechstein, R. and Kühnle, A.: Atomic structure and water arrangement on K-feldspar microcline (001), accepted in Nanoscale, DOI:10.1039/d3nr05585j, 2024.Kiselev, A., Bachmann, F., Pedevilla, P., Cox, S. J., Michaelides, A., Gerthsen, D., and Leisner, T.: Active sites in heterogeneous ice nucleation—the example of K-rich feldspars, Science, 355, 367–371, 2017.Soni, A. and Patey, G. N.: Simulations of water structure and the possibility of ice nucleation on selected crystal planes of K-feldspar, J. Chem. Phys., 150, 214501, 2019.