Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics.

Gabriel V Lau,George Jackson,Ian J Ford,Patricia A Hunt,Erich A Müller

doi:10.1063/1.4935198

Gabriel V Lau, George Jackson + Show 3 more

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https://doi.org/10.1063/1.4935198

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Abstract

Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study.

Highlights

Atmospheric aerosols play a key role in climate, weather, pollution and human health
The most important quantity in nucleation modelling within a traditional kinetic/thermodynamic framework is the excess free energy which is often interpreted as the cost in free energy associated with the formation of the interface between the two phases
In classical nucleation theory (CNT) of a liquid cluster forming from a supersaturated vapour, the excess free energy Fs is one of the two terms that comprise the work of cluster formation φ: φ = Fs − N ∆μ, (1)

Summary

Introduction

Atmospheric aerosols play a key role in climate, weather, pollution and human health. These substances can influence the optical properties of clouds as well as their lifetimes and have an effect on the distribution of precipitation and the global radiation budget (the difference between solar energy accumulated by the earth and the energy radiated into space). Important progress has been made in recent years in identifying the species responsible for the initial stages of aerosol formation in the the atmosphere [11,12,13,14,15] but the task of properly characterising the formation mechanism in detail still remains, understanding the population dynamics and thermodynamics of the molecular clusters in question. In classical nucleation theory (CNT) of a liquid cluster forming from a supersaturated vapour, the excess free energy Fs is one of the two terms that comprise the work of cluster formation φ:

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