Kinetics of Heterogeneous Nucleation in Supersaturated Vapor: Fundamental Limits to Neutral Particle Detection Revisited

We examine the nucleated (with barrier) activation of perfectly wetting (zero contact angle) particles ranging from essentially bulk size down to approximately 1-nm mass diameter. While similar studies trace back to the pioneering work of Fletcher, we present here a novel approach to the analysis based on general area constructions that enable key thermodynamic properties, including surface and bulk contributions to nucleation work, to be interpreted geometrically with reference to the Kelvin curve. The kinetics of activation are described in more detail in terms of the mean first passage time (MFPT) for barrier crossing. MFPT theory and benchmark calculations are used to develop and test a new approximate-but-simpler-to-use analytic expression for the barrier crossing rate. The present study is motivated by recent condensation particle counter (CPC) studies that appear to finally establish the long-predicted detection of "sub-Kelvin" particles in the nanosize regime. Corresponding states thermodynamic and kinetic scaling approaches are used to facilitate the correlation and selection of optimal CPC working fluids and operating conditions based on a new metric for heterogeneous nucleation, the signal-to-noise ratio, and physical and chemical properties.