abstract
Ketones are some of the most widely used solvents, with a variety of applications. In addition, molecules with ketone functional groups feature prominently in pharmaceutical APIs. However, they present a particular challenge for modelling, particularly when considering solutions and mixtures. In this paper, we present a new classical nonpolarizable model for ketones, based on our recently-proposed Polarization-Consistent Approach (PolCA). PolCA is based on a theoretically-grounded consideration of polarization effects in a nonpolarizable framework, which lead to an optimal selection of the model's effective dipole moment and point charges, as well as to the derivation of post facto corrections for solvation free energy and dielectric constant predictions. This allows us to effectively account for the missing effects of polarization in a computationally expedient way. At the core of this approach is a realistic estimate of the dipole moment of ketones in the liquid phase, which we obtain by applying the recently-developed Self-Consistent Electrostatic Embedding (SCEE) method. The new model, developed under this paradigm, provides significantly improved predictions over the state-of-the-art TraPPE model, and shows improved transferability to heterogeneous systems.
keywords
PREDICTING HYDROPHOBIC SOLVATION; UNITED-ATOM DESCRIPTION; PHASE-EQUILIBRIA; DIPOLE-MOMENT; TRANSFERABLE POTENTIALS; DIELECTRIC-CONSTANT; MODEL; ACETONE; SIMULATION; MIXTURES
subject category
Chemistry; Physics
authors
Barrera, MC; Cree, J; Gomes, JRB; Jorge, M
our authors
José R. B. Gomes
Principal ResearcherProjects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
MCB acknowledges the University of Strathclyde for a PhD stu- dentship. The authors thank Daniel J. Cole for helpful discussions during the preparation of this manuscript. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 and LA/P/0006/2020, financed by national funds through the FCT/MCTES (PIDDAC) .