The Statistical Mechanics
of Solution-Phase Nucleation:
CaCO 3 Revisited
Evgenii O. Fetisov, Marcel D. Baer, J. Ilja Siepmann, Gregory K. Schenter,
Shawn M. Kathmann, and Christopher J. Mundy
1 Introduction
In this review, we focus on the development of both theoretical and simulation frameworks to understand the initial stages of homogeneous nucleation in solutions. To
date, the vast majority of solution-phase nucleation studies have been performed on
model systems [1]. These pioneering studies have showcased the use of statistical
mechanical sampling methods in conjunction with the classical nucleation theory
(CNT) to provide more detail than CNT provides alone. Exceptions of this are in
the area of vapor phase nucleation studies that utilize modern empirical or quantum
mechanical interaction potentials in conjunction with advanced sampling approaches
and theory to describe the nucleation of a liquid from a supersaturated vapor [2]. Complexity is encountered when extending theory and simulation developed for the vapor
phase into the solution phase. This is because the nucleating species are surrounded
by solvent molecules and the configurations and energy distribution of the entire statistical assembly must be considered. Furthermore, it is essential to understand how
to define the “cluster” of the new phase as its definition is equivalent to defining a
reaction coordinate for a phase transformation. The solution phase may also provide
E. O. Fetisov · M. D. Baer · G. K. Schenter · S. M. Kathmann · C. J. Mundy
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory,
Richland, WA 99354, USA
J. I. Siepmann
Department of Chemistry and Chemical Theory Center, University of Minnesota, 207 Pleasant
Street SE, Minneapolis, MN 55455, USA
Department of Chemical Engineering and Materials Science, University of Minnesota, 421
Washington Avenue SE, Minneapolis, MN 55455, USA
C. J. Mundy (B)
Department of Chemical Engineering, University of Washington, Seattle, WA 98195, USA
e-mail: chris.mundy@pnnl.gov
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
E. J. Maginn and J. Errington (eds.), Foundations of Molecular Modeling
and Simulation, Molecular Modeling and Simulation,
https://doi.org/10.1007/978-981-33-6639-8_5
101
of Solution-Phase Nucleation:
CaCO 3 Revisited
Evgenii O. Fetisov, Marcel D. Baer, J. Ilja Siepmann, Gregory K. Schenter,
Shawn M. Kathmann, and Christopher J. Mundy
1 Introduction
In this review, we focus on the development of both theoretical and simulation frameworks to understand the initial stages of homogeneous nucleation in solutions. To
date, the vast majority of solution-phase nucleation studies have been performed on
model systems [1]. These pioneering studies have showcased the use of statistical
mechanical sampling methods in conjunction with the classical nucleation theory
(CNT) to provide more detail than CNT provides alone. Exceptions of this are in
the area of vapor phase nucleation studies that utilize modern empirical or quantum
mechanical interaction potentials in conjunction with advanced sampling approaches
and theory to describe the nucleation of a liquid from a supersaturated vapor [2]. Complexity is encountered when extending theory and simulation developed for the vapor
phase into the solution phase. This is because the nucleating species are surrounded
by solvent molecules and the configurations and energy distribution of the entire statistical assembly must be considered. Furthermore, it is essential to understand how
to define the “cluster” of the new phase as its definition is equivalent to defining a
reaction coordinate for a phase transformation. The solution phase may also provide
E. O. Fetisov · M. D. Baer · G. K. Schenter · S. M. Kathmann · C. J. Mundy
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory,
Richland, WA 99354, USA
J. I. Siepmann
Department of Chemistry and Chemical Theory Center, University of Minnesota, 207 Pleasant
Street SE, Minneapolis, MN 55455, USA
Department of Chemical Engineering and Materials Science, University of Minnesota, 421
Washington Avenue SE, Minneapolis, MN 55455, USA
C. J. Mundy (B)
Department of Chemical Engineering, University of Washington, Seattle, WA 98195, USA
e-mail: chris.mundy@pnnl.gov
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
E. J. Maginn and J. Errington (eds.), Foundations of Molecular Modeling
and Simulation, Molecular Modeling and Simulation,
https://doi.org/10.1007/978-981-33-6639-8_5
101