ABSTRACT
Despite the intense activity at electronic and atomistic resolutions, coarse grained (CG) modeling of metal-organic frameworks remains largely unexplored. One of the main reasons for this is the lack of adequate CG force fields. In this work, we present iterative Boltzmann inversion and force matching (FM) force fields for modeling ZIF-8 at three different coarse grained resolutions. Their ability to reproduce structure, elastic tensor, and thermal expansion is evaluated and compared with that of MARTINI force fields considered in previous work [Alvares et al., J. Chem. Phys. 158, 194107 (2023)]. Moreover, MARTINI and FM are evaluated for their ability to depict the swing effect, a subtle phase transition ZIF-8 undergoes when loaded with guest molecules. Overall, we found that all our force fields reproduce structure reasonably well. Elastic constants and volume expansion results are analyzed, and the technical and conceptual challenges of reproducing them are explained. Force matching exhibits promising results for capturing the swing effect. This is the first time these CG methods, widely applied in polymer and biomolecule communities, are deployed to model porous solids. We highlight the challenges of fitting CG force fields for these materials.
ABSTRACT
In this contribution, the well-known MARTINI particle-based coarse graining approach is tested for its ability to model the ZIF-8 metal-organic framework. Its capability to describe structure, lattice parameters, thermal expansion, elastic constants and amorphization is evaluated. Additionally, the less coarsened models were evaluated for reproducing the swing effect and the host-guest interaction energies were analyzed. We find that MARTINI force fields successfully capture the structure of the Metal-Organic Framework (MOF) for different degrees of coarsening, with the exception of the MARTINI 2.0 models for the less coarse mapping. MARTINI 2.0 models predict more accurate values of C11 and C12, while MARTINI 3.0 has a tendency to underestimate them. Among the possibilities tested, the choice of bead flavors within a particular MARTINI version appears to have a less critical impact in the simulated properties of the empty framework. None of the coarse-grained (CG) models investigated were able to capture the amorphization nor the swing effect within the scope of MD simulations. A perspective on the importance of having a proper Lennard-Jones (LJ) parametrization for modeling guest-MOF and MOF-MOF interactions is highlighted.
ABSTRACT
Calcium aluminotitanate (CaO-Al2O3-TiO2) ternary oxides are of fundamental interest in Materials as well as Earth and environmental science, and a key system for several industrial applications. As their properties at the atomic scale are scarcely known, interionic interactions for the melts are built from a bottom up strategy consisting in fitting first only Al2O3, CaO and TiO2single oxide compounds separately with a unified description of the oxygen charge and O-O interaction term. For this purpose, a mean-square difference minimization of the partial pair-correlation functions with respect to theab initioreference was performed. The potentials for the ternary oxide are finally built straightforwardly by adding purely Coulomb terms for dissimilar cation-cation interactions without further fit. This general and unified approach is transferable and successfully describes the structural and diffusion properties of the three single oxides as well as the ternary melts simultaneously. A possible underlying structural mechanism at the origin of the diffusion evolution with TiO2content is proposed based on the formation of Ti induced triply bonded oxygen.
ABSTRACT
A detailed theoretical study of CaO in the solid and liquid states by means of combined classical and ab initio molecular dynamics simulations is presented. Evolution of the specific heat capacity at constant pressure as a function of temperature is studied, and the melting temperature and enthalpy of fusion are determined. It is shown that an empirical Born-Mayer-Huggins potential gives a good representation of pure CaO in the liquid and solid states as compared to available experimental data and density functional theory calculations. Consistency of the predicted results obtained for CaO with the data available in commercial thermodynamic databases and experimental values in the literature is discussed. The present methodology and theoretical results provide a new accurate basis for calculations of thermodynamic properties in a temperature range that is hardly accessible by experiments.
