In this work, we revisit the classic problem of homogeneous nucleation of a liquid droplet in a supersaturated vapor phase. We consider this at different extents of the driving force, or equivalently the supersaturation, and calculate a reaction coordinate (RC) for nucleation as the driving force is varied. The RC is constructed as a linear combination of three order parameters, where one accounts for the number of liquidlike atoms and the other two for local density fluctuations. The RC is calculated from biased and unbiased molecular dynamics (MD) simulations using the spectral gap optimization approach “SGOOP” [P. Tiwary and B. J. Berne, Proc. Natl. Acad. Sci. U. S. A. 113, 2839 (2016)]. Our key finding is that as the supersaturation decreases, the RC ceases to simply be the number of liquidlike atoms, and instead, it becomes important to explicitly consider local density fluctuations that correlate with shape and density variations in the nucleus. All three order parameters are found to have similar barriers in their respective potentials of mean force; however, as the supersaturation decreases, the density fluctuations decorrelate slower and thus carry longer memory. Thus, at lower supersaturations, density fluctuations are non-Markovian and cannot be simply ignored from the RC by virtue of being noise. Finally, we use this optimized RC to calculate nucleation rates in the infrequent metadynamics framework and show that it leads to a more accurate estimate of the nucleation rate with four orders of magnitude acceleration relative to unbiased MD.

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