Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userSimulations of Crystal Nucleation from Solution at Constant Chemical Potential
62
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
A widely spread method of crystal preparation is to precipitate it from a supersaturated solution. In such a process, control of solution concentration is of paramount importance. Nucleation process, polymorph selection, and crystal habits depend crucially on this thermodynamic parameter. When performing simulations in the canonical ensemble as the crystalline phase is deposited the solution is depleted of solutes. This unavoidable modification of the thermodynamic conditions leads to significant artifact. Here we adopt the idea of the constant chemical potential molecular dynamics approach of Perego et al. [J. Chem. Phys. 2015, 142, 144113] to the study of nucleation. Our method allows determining the crystal nucleus size and nucleation rates at constant supersaturation. As an example we study the homogeneous nucleation of sodium chloride from its supersaturated aqueous solution.
rate research
Read More
Molecular Dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, which range from nano-technology to pharmaceutical chemistry. However, these calculations are affected by severe finite-size effects, such as the solution being depleted as the chemical process proceeds, which influence the outcome of the simulations. To overcome these limitations, one must allow the system to exchange molecules with a macroscopic reservoir, thus sampling a Grand-Canonical ensemble. Despite the fact that different remedies have been proposed, this still represents a key challenge in molecular simulations. In the present work we propose the Constant Chemical Potential Molecular Dynamics (C$mu$MD) method, which introduces an external force that controls the environment of the chemical process of interest. This external force, drawing molecules from a finite reservoir, maintains the chemical potential constant in the region where the process takes place. We have applied the C$mu$MD method to the paradigmatic case of urea crystallization in aqueous solution. As a result, we have been able to study crystal growth dynamics under constant supersaturation conditions, and to extract growth rates and free-energy barriers.
Accurate prediction of a gas solubility in a liquid is crucial in many areas of chemistry, and a detailed understanding of the molecular mechanism of the gas solvation continues to be an active area of research. Here, we extend the idea of constant chemical potential molecular dynamics (C{mu}MD) approach to the calculation of the gas solubility in the liquid under constant gas chemical potential conditions. As a representative example, we utilize this method to calculate the isothermal solubility of carbon dioxide in water. Additionally, we provide microscopic insight into the mechanism of solvation that preferentially occurs in areas of the surface where the hydrogen network is broken.
Within the reweighting approach, one has the freedom to choose the Monte Carlo action so that it provides a good overlap with the finite-mu measure but remains simple to simulate. We explore several choices of action in the regime of small mu. Simulating with a finite isospin chemical potential mu_I=mu gives a better overlap than the standard choice mu=0, with no computational overhead.
We provide the most accurate results for the QCD transition line so far. We optimize the definition of the crossover temperature $T_c$, allowing for its very precise determination, and extrapolate from imaginary chemical potential up to real $mu_B approx 300$ MeV. The definition of $T_c$ adopted in this work is based on the observation that the chiral susceptibility as a function of the condensate is an almost universal curve at zero and imaganiary $mu_B$. We obtain the parameters $kappa_2=0.0153(18)$ and $kappa_4=0.00032(67)$ as a continuum extrapolation based on $N_t=10,12$ and $16$ lattices with physical quark masses. We also extrapolate the peak value of the chiral susceptibility and the width of the chiral transition along the crossover line. In fact, both of these are consistent with a constant function of $mu_B$. We see no sign of criticality in the explored range.
A quantitative understanding of the evaporative drying kinetics and nucleation rates of aqueous based aerosol droplets is important for a wide range of applications, from atmospheric aerosols to industrial processes such as spray drying. Here, we introduce a numerical model for interpreting measurements of the evaporation rate and phase change of drying free droplets made using a single particle approach. We explore the evaporation of aqueous sodium chloride and sodium nitrate solution droplets. Although the chloride salt is observed to reproducibly crystallise at all drying rates, the nitrate salt solution can lose virtually all of its water content without crystallising. The latter phenomenon has implications for our understanding of the competition between the drying rate and nucleation kinetics in these two systems. The nucleation model is used in combination with the measurements of crystallisation events to infer nucleation rates at varying equilibrium state points, showing that classical nucleation theory provides a good description of the crystallisation of the chloride salt but not the nitrate salt solution droplets. The reasons for this difference are considered.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
