The Statistical Mechanics of Solution-Phase Nucleation: CaCO$$_3$$ Revisited

Fetisov, Evgenii O.; Baer, Marcel D.; Siepmann, J. Ilja; Schenter, Gregory K.; Kathmann, Shawn M.; Mundy, Christopher J.

doi:10.1007/978-981-33-6639-8_5

Cited by 3 publications

(2 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Interactions between multivalent cations and phosphate anions play critical roles in determining the structure of DNA/RNA, − the catalytic activity of DNA- and RNA-based enzymes, − and the structure and function of many other biomolecular and biomimetic systems. , In addition, the interactions between phosphate and calcium ions play an important role in the nucleation and growth of calcium phosphate minerals, such as the biomineral hydroxyapatite, and similar interactions are important for a wide range of minerals. − In this broad array of processes, the interactions between metal cations and phosphate anions occur in and are mediated by liquid water. Consequently, a molecular-scale understanding of the role of water is needed to understand and control processes ranging from DNA enzyme activity to mineral growth.…”

Section: Polar and Charged Polyatomic Solutesmentioning

confidence: 99%

Local Molecular Field Theory for Coulomb Interactions in Aqueous Solutions

2023

View full text Add to dashboard Cite

Coulomb interactions play a crucial role in a wide array of processes in aqueous solutions but present conceptual and computational challenges to both theory and simulations. We review recent developments in an approach addressing these challengeslocal molecular field (LMF) theory. LMF theory exploits an exact and physically suggestive separation of intermolecular Coulomb interactions into strong short-range and uniformly slowly varying long-range components. This allows us to accurately determine the averaged effects of the long-range components on the short-range structure using effective single particle fields and analytical corrections, greatly reducing the need for complex lattice summation techniques used in most standard approaches. The simplest use of these ideas in aqueous solutions leads to the short solvent (SS) model, where both solvent–solvent and solute–solvent Coulomb interactions have only short-range components. Here we use the SS model to give a simple description of pairing of nucleobases and biologically relevant ions in water.

show abstract

Section: Polar and Charged Polyatomic Solutesmentioning

confidence: 99%

Local Molecular Field Theory for Coulomb Interactions in Aqueous Solutions

2023

View full text Add to dashboard Cite

show abstract

“…This resulting hydrated CaCO 3 dense phase, i.e., hydrated ACC (Fig. 4e), will transform into a stable CaCO 3 polymorph by expelling water 35 . Although this last important transformation cannot be directly simulated, the characterization of the resulting ACC from simulated data with ab initio based interaction potentials falls in the experimental range of ACC solubility 35 .…”

Section: S8fmentioning

confidence: 99%

Formation, Chemical Evolution, and Solidification of the Calcium Carbonate Dense Liquid Phase

DeYoreo

Jin

Chen

et al. 2022

Preprint

View full text Add to dashboard Cite

Nucleation is the seminal event in crystallization and predicting its progression is a key challenge across diverse scientific fields. Although classical nucleation theory successfully describes some systems, it fails to do so in a growing list of materials due to free energetic and kinetic complexities1. In particular, when systems are driven far from equilibrium, the high chemical potential opens pathways that pass through metastable polymorphs, amorphous states, and even dense liquid phases that can form absent the energy barrier normally opposing nucleation1-5. CaCO3 provides a canonical example6-8; following discovery of the CaCO3 “polymer-induced liquid precursor”9,10, which forms upon introduction of poly-ionic polymers10-12 like polyacrylic acid13,14, numerous studies have concluded that even pure CaCO3 possesses a dense liquid phase. This phase — likely stabilized by poly-ionic proteins15-19 — is proposed to serve as a precursor to biomineral formation15, transforming first to the amorphous phase and then to crystalline products3,20-22. Yet little is known about the mechanisms of CaCO3 dense liquid formation and solidification, its composition is unknown, and its relationship to the polymer-induced liquid-precursor remains unclear. Using in situ methods, we show that this phase forms by spinodal decomposition, is a bicarbonate comprised of 1Ca2+:2HCO3-:7±2H2O, and transforms to hollow particles of hydrated amorphous CaCO3 with the release of CO2 and H2O. Acidic proteins and polymers extend liquid phase lifetimes but leave this chemical pathway unchanged. Molecular simulations suggest the liquid phase forms via direct condensation of solvated Ca2+•(HCO3-)2 complexes that react due to proximity effects in the confinement of the liquid droplets. The findings provide an in-depth picture of CaCO3 nucleation via liquid-liquid phase separation, elucidating an often-proposed pathway by which nature orchestrates the complex process of biomineralization.

show abstract