Reliable Structural, Energetic and Reactivity Predictions for Molecular Radicals, Ions and Neutrals by ab initio Theory

This project involves high-level ab initio theoretical studies on hydrocarbon halides, nitrogen oxides, and the organic carboxylate anions. The researchers intend to obtain structural and spectroscopic information such as vibrational frequencies of these chemical species, and energetic data such as heats of formation at the coupled-cluster level with the one-electron correlation extrapolated to the complete basis set limit. The thermochemistry predictions on hydrocarbon halides and gaseous nitrogen oxides will be useful in establishing the kinetic model for relevant simulations in atmospheric and combustion chemistry. In cases where the spectroscopic constants and thermochemical data are not known, the researchers’ high-level theoretical predictions will provide a reliable and self-consistent set of thermochemical data and structural information to the chemistry community. The theoretical methods for anionic species have not been thoroughly established. In this work, the researchers aim at extending and benchmarking their current theoretical methods for reliable thermochemical and structural predictions on the organic carboxylate anions through the comparison between computational and existing experimental data. This part of the work is intended to provide reliable thermochemical data for biological/chemical systems involving carboxylic acids and derivatives.