Water activity and shear viscosity of water–glyceline mixtures are important process parameters that can be effectively calculated using molecular modelling.
Five molecular models for trimethylamine N-oxide (TMAO) to be used in conjunction with compatible models for liquid water are evaluated by comparison of molecular dynamics (MD) simulation results to experimental data as functions of TMAO molality. The experimental data comprise thermodynamic properties (density, apparent molar volume, and partial molar volume at infinite dilution), transport properties (self-diffusion and shear viscosity), structural properties (radial distribution functions and degree of hydrogen bonding), and dielectric properties (dielectric spectra and static permittivity). The thermodynamic and transport properties turned out to be useful in TMAO model discrimination while the influence of the water model and the TMAO-water interaction are effectively probed through the calculation of dielectric spectra.
The key to nanoscale control of physical, chemical, and biological processes lies in well‐founded models of noncovalent binding. Atomistic simulations probe the free‐energy surface underlying molecular assembly processes in solution. Two examples of noncovalent binding studied by molecular dynamics simulations are discussed, the dimerization of a water‐soluble perylene bisimide derivative in aqueous solution with a focus on the influence of solvent composition on the aggregation strength and the binding of 1‐butanol to α‐cyclodextrin at infinite dilution with the focus on the determination of method‐independent binding free energies.
This study extends the transferable
anisotropic Mie potential (TAMie)
to 1-alcohols. Force-field parameters are adjusted by minimizing squared
deviations of calculated vapor pressures and liquid densities from
experimental data of 1-propanol, 1-butanol, and 1-pentanol. The force
field leads to small average absolute deviations of 1% in vapor pressures
and 0.6% in liquid densities for temperature ranges of 0.58 ≤ T/T
exp
c ≤ 0.96, relative to experimental critical
temperatures. The force field is transferable to higher 1-alcohols,
as shown for 1-hexanol to 1-octanol. Individual parameter sets are
provided for methanol and ethanol. Dynamic properties, such as shear
viscosity and self-diffusion coefficients of pure substances, are
predicted with fair agreement with experimental data, considering
that no dynamic property has entered the parameterization. Further,
the phase behavior of binary mixtures of primary alcohols with alkanes
is studied, and predictions of the TAMie model are found in very good
agreement with experimental data.
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