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Creators/Authors contains: "Yuan, Tianmu"

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  1. Heterogeneous nucleation is the dominant form of liquid-to-solid transition in na- ture. Although molecular simulations are most uniquely suited to study nucleation, the waiting time to observe even a single nucleation event can easily exceed current computational capabilities. Therefore, there exists an imminent need for methods that enable computationally fast and feasible studies of heterogeneous nucleation. Seeding is a technique that has proven successful at dramatically expanding the range of computationally accessible nucleation rates in simulation studies of ho- mogeneous crystal nucleation. In this paper, we introduce a new seeding method for heterogeneous nucleation called Rigid Seeding (RSeeds). Crystalline seeds are treated as pseudo-rigid bodies and simulated on a surface with metastable liquid above its melting temperature. This allows the seeds to adapt to the surface and identify favorable seed–surface configurations, which is necessary for reliable predictions of crystal polymorphs that form and the corresponding heterogeneous nucle- ation rates. We demonstrate and validate RSeeds for heterogeneous ice nucleation on a flexible self-assembled monolayer surface, a mineral surface based on kaolinite, and two model surfaces. RSeeds predicts the correct ice polymorph, exposed crystal plane, and rotation on the surface. RSeeds is semiquantitative and can be used to estimate the critical nucleus size and nucleation rate when combined with classical nucleation theory. We demonstrate that RSeeds can be used to evaluate nucleation rates spanning many orders of magnitude. 
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