Development of computational design for reliable prediction of dielectric strengths of perfluorocarbon compounds.

The development of robust computational protocols capable of accurately predicting the dielectric strengths of eco-friendly insulating gas candidates is crucial; however, it lacks relevant efforts significantly. Consequently, a series of computational protocols are employed in this study to enable the computational prediction of polarizability and ionization energy of eco-friendly, perfluorinated carbon-based candidates, followed by the equation-based prediction of their dielectric strength. The validation process associated with the prediction of the afore-mentioned variables for selected datasets confirms the suitability of the B3LYP-based prediction protocol for reproducing experimental values. Subsequently, the validation of dielectric strength prediction outlines the following three conclusions. (1) The referenced equation adopted from a previous study is incapable of predicting the dielectric strengths of 137 organic compounds present in our database. (2) Parameterization of the coefficients in the referenced equation leads to the accurate prediction of the dielectric strengths. (3) Incorporation of a novel variable, viz. molecular weight, into the referenced equation combined with the parameterization of the coefficients leads to a robust protocol capable of predicting dielectric strengths with high efficiencies even with a significantly smaller fitting dataset. This implies the development of a comprehensive solution capable of accurately predicting the dielectric strengths of a substantially large dataset.

Insights on Redox Properties of Sumanene Derivatives for High-Performance Organic Cathodes.

Despite the potential of large organic molecules for insoluble cathode materials in lithium-ion batteries, they have attracted less attention owing to the penalty in the molecular weight. Herein, an advanced computational modeling approach is employed to comprehensively explore the electrochemical characteristics and theoretical charge/energy storage capability for a series of sumanene derivatives. It is highlighted from this investigation that the carbonyl moiety is generally beneficial to the improvement of the redox properties for the sumanenes. The sumanene with hexagon rings fully functionalized by six carbonyls particularly exhibits both the remarkably high redox potential (3.53 V vs Li/Li+) and performance parameters (454 mAh/g and 1129 mWh/g), implying its candidacy as high-potential organic cathodes. It is further demonstrated from a universal relationship of redox potential-electronic property-solvation property that a sumanene derivative would experience a two-stage discharging behavior. This indicates that the sumanene derivative would be cathodically inactive due to a sudden increase of solvation energy.

Improving the Understanding of the Redox Properties of Fluoranil Derivatives for Cathodes in Sodium-Ion Batteries.

Despite the potential of organic cathodes in sodium-ion batteries, their redox properties still need to be explored. In this study, a density functional theory modeling approach is employed to comprehensively investigate the redox properties and theoretical performance parameters for a selected set of fluoranil derivatives as cathode materials. The redox properties are further correlated with various characteristics including structural variations, electronic properties, and solvation. Three primary conclusions are drawn. First, the incorporation of bulky trifluoromethyl functional group(s) into fluoranil increases its redox potential but significantly decreases its gravimetric charge capacity. This suggests that the trifluoromethyl functional group(s) would be detrimental to the design of high-performance batteries. Second, fluoranil exhibits significant enhancements in terms of redox properties and theoretical performance compared with its hydrogenated form, benzoquinone, suggesting a desired strategy for designing high-performance batteries. Third, the redox properties of fluoranil derivatives would strongly rely not only on structural variations (e.g., bulkiness) and electronic properties (e.g., functionality) but also on solvation energy. It is further verified that cathodic deactivation could be completed by solvation energy. The new understanding will provide us with guidelines for an efficient design of promising organic cathode materials.