TY - JOUR
T1 - Accelerated Nucleation Due to Trace Additives
T2 - A Fluctuating Coverage Model
AU - Poon, Geoffrey G.
AU - Peters, Baron
N1 - Funding Information:
The authors thank Peter Vekilov, Joop ter Horst, Richard Sear, Wenhao Sun, Marco Mazzotti, James J. De Yoreo, and Valeria Molinero for helpful comments and discussions. G.G.P. thanks the National Science Foundation (NSF) for support through the Graduate Research Fellowship under DGE 1144085. B.P. was supported by a Camille Dreyfus Teacher - Scholar award.
Publisher Copyright:
© 2015 American Chemical Society.
PY - 2016/3/3
Y1 - 2016/3/3
N2 - We develop a theory to account for variable coverage of trace additives that lower the interfacial free energy for nucleation. The free energy landscape is based on classical nucleation theory and a statistical mechanical model for Langmuir adsorption. Dynamics are modeled by diffusion-controlled attachment and detachment of solutes and adsorbing additives. We compare the mechanism and kinetics from a mean-field model, a projection of the dynamics and free energy surface onto nucleus size, and a full two-dimensional calculation using Kramers-Langer-Berezhkovskii-Szabo theory. The fluctuating coverage model predicts rates more accurately than mean-field models of the same process primarily because it more accurately estimates the potential of mean force along the size coordinate.
AB - We develop a theory to account for variable coverage of trace additives that lower the interfacial free energy for nucleation. The free energy landscape is based on classical nucleation theory and a statistical mechanical model for Langmuir adsorption. Dynamics are modeled by diffusion-controlled attachment and detachment of solutes and adsorbing additives. We compare the mechanism and kinetics from a mean-field model, a projection of the dynamics and free energy surface onto nucleus size, and a full two-dimensional calculation using Kramers-Langer-Berezhkovskii-Szabo theory. The fluctuating coverage model predicts rates more accurately than mean-field models of the same process primarily because it more accurately estimates the potential of mean force along the size coordinate.
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U2 - 10.1021/acs.jpcb.5b08510
DO - 10.1021/acs.jpcb.5b08510
M3 - Article
AN - SCOPUS:84960192366
SN - 1520-6106
VL - 120
SP - 1679
EP - 1684
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 8
ER -