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Critical clusters in liquid condensation have a different density than bulk liquid. A new theory incorporating cluster density accurately predicts nucleation, improving our understanding of this process.

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Area of Science:

  • Physical Chemistry
  • Computational Physics
  • Materials Science

Background:

  • Nucleation is fundamental to phase transitions, including liquid condensation.
  • Classical nucleation theory often assumes critical clusters have bulk liquid density, a simplification potentially limiting accuracy.

Purpose of the Study:

  • To precisely characterize droplet nucleation from supersaturated gas using advanced simulations.
  • To investigate the density of critical clusters during nucleation.
  • To develop and validate a refined nucleation theory.

Main Methods:

  • State-of-the-art rare-event sampling simulations were employed.
  • Atomistic simulations were used to observe nucleation pathways.
  • A two-variable nucleation theory, accounting for cluster density, was developed and tested.

Main Results:

  • Critical clusters were found to have a density significantly different from bulk liquid.
  • A nonclassical nucleation pathway involving simultaneous growth and densification was observed.
  • The two-variable nucleation theory quantitatively reproduced simulation results for nucleation rates and critical properties.

Conclusions:

  • Cluster density is a critical variable in nucleation phenomena.
  • The developed two-variable theory offers a more accurate description of nucleation pathways and rates.
  • This work refines nucleation theory by moving beyond single-variable approximations.