Nonclassical Nucleation Pathways in Liquid Condensation Revealed by Simulation and Theory

Using state-of-the-art rare-event sampling simulations, we precisely characterize the nucleation of liquid droplets from a supersaturated Lennard-Jones gas and uncover a key physical feature: critical clusters nucleate with a density that differs substantially from that of the macroscopic equilibrium liquid. Our atomistic simulations also reveal a nonclassical nucleation pathway showing simultaneous growth and densification in liquid condensation. We then exploit these insights to develop a two-variable nucleation theory, in which the cluster density is allowed to vary. Our accessible model based on the capillary approximation is able to quantitatively retrieve the numerical results in nucleation rate and critical cluster properties over a large range of supersaturation. Remarkably, the two-variable model successfully captures the observed nucleation pathway. The effectiveness of this integrated numerical and theoretical framework demonstrates that the cluster density is a decisive variable in nucleation, highlighting the limitations of the single-variable description while offering a robust foundation for its refinement.