Depleting Nucleation: Out-of-Equilibrium Effects of Monomer Consumption and System Adiabaticity on the Activation Energy Barrier
- 1Department of Chemistry & Biochemistry, Villanova University, 800 E. Lancaster Avenue, Villanova, PA, USA, 19085
- 2Materials Science and Therapeutics Group, Schrödinger, Inc., 1540 Broadway, 24th floor, New York, NY, USA, 10036
Abstract
This work challenges two common assumptions of Classical Nucleation Theory (CNT), namely, isothermal conditions and a constant supply of monomers, which can lead to inaccuracies in predicting nucleation rates in small, well-insulated systems. Given the contemporary focus on synthesizing nanoparticles and nanocrystals for various industrial applications, a re-examination of how these factors impact the activation energy of nucleation is warranted. A more accurate relationship is proposed to account for the selfheating that occurs in thermally insulated systems. Furthermore, to address the effect of monomer consumption by cluster formation, the Gibbs-Thomson equation is incorporated into the existing theoretical framework to describe the increase in the activation energy that accompanies supersaturation relief. The newly proposed equation simultaneously helps reconcile the recent observation that the CNT-predicted energy barrier is systematically underestimated by a factor of approximately 1.78 [Skrdla, P. J. "A Theoretical Approach for Modeling Non-steady-state Nucleation Kinetics in Solutions and Melts." J. Phys. Chem. C 130 (2026): 3614–3623]. Although the condensation of water is used as a case study, the methodologies presented are broadly applicable to any nucleating system operating under the constraints of finite volume and adiabaticity.
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BibTeX
@misc{skrdla2026depleting,
title = {{Depleting Nucleation: Out-of-Equilibrium Effects of Monomer Consumption and System Adiabaticity on the Activation Energy Barrier}},
author = {Peter J. Skrdla},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008689/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008689/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Depleting Nucleation: Out-of-Equilibrium Effects of Monomer Consumption and System Adiabaticity on the Activation Energy Barrier
AU - Peter J. Skrdla
PY - 2026
DA - 2026/09/11
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008689/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008689/v1
AB - This work challenges two common assumptions of Classical Nucleation Theory (CNT), namely, isothermal conditions and a constant supply of monomers, which can lead to inaccuracies in predicting nucleation rates in small, well-insulated systems. Given the contemporary focus on synthesizing nanoparticles and nanocrystals for various industrial applications, a re-examination of how these factors impact the activation energy of nucleation is warranted. A more accurate relationship is proposed to account for the selfheating that occurs in thermally insulated systems. Furthermore, to address the effect of monomer consumption by cluster formation, the Gibbs-Thomson equation is incorporated into the existing theoretical framework to describe the increase in the activation energy that accompanies supersaturation relief. The newly proposed equation simultaneously helps reconcile the recent observation that the CNT-predicted energy barrier is systematically underestimated by a factor of approximately 1.78 [Skrdla, P. J. "A Theoretical Approach for Modeling Non-steady-state Nucleation Kinetics in Solutions and Melts." J. Phys. Chem. C 130 (2026): 3614–3623]. Although the condensation of water is used as a case study, the methodologies presented are broadly applicable to any nucleating system operating under the constraints of finite volume and adiabaticity.
ER -