PNAS 119 28 (2022)
Nonisothermal nucleation in the gas phase is driven by cool subcritical clusters
Valtteri Tikkanena, Bernhard Reischla , Hanna Vehkamäkia, and Roope Halonenb,c,*
a Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki FI-00014, Finland
b Center for Joint Quantum Studies, School of Science, Tianjin University, Tianjin 300072, China
c Department of Physics, School of Science, Tianjin University, Tianjin 300072, China
* E-mail: roope@tju.edu.cn
Abstract
Nucleation of clusters from the gas phase is a widely encountered phenomenon, yet rather little is understood about the underlying out-of-equilibrium dynamics of this process. The classical view of nucleation assumes isothermal conditions where the nucleating clusters are in thermal equilibrium with their surroundings. However, in all first-order phase transitions, latent heat is released, potentially heating the clusters and suppressing the nucleation. The question of how the released energy affects cluster temperatures during nucleation as well as the growth rate remains controversial. To investigate the nonisothermal dynamics and energetics of homogeneous nucleation, we have performed molecular dynamics simulations of a supersaturated vapor in the presence of thermalizing carrier gas. The results obtained from these simulations are compared against kinetic modeling of isothermal nucleation and classical nonisothermal theory. For the studied systems, we find that nucleation rates are suppressed by two orders of magnitude at most, despite substantial release of latent heat. Our analyses further reveal that while the temperatures of the entire cluster size populations are elevated, the temperatures of the specific clusters driving the nucleation flux evolve from cold to hot when growing from subcritical to supercritical sizes and resolve the apparent contradictions regarding cluster temperatures. Our findings provide unprecedented insight into realistic nucleation events and allow us to directly assess earlier theoretical considerations of nonisothermal nucleation.
