Reliable thermochemistry predictions are vital to understanding reactivity and stability, and are important contributions from computational chemistry. Main group computational thermochemistry can now routinely achieve predictions within 1 kcal/mol of experimental values, and, for some small molecules, accuracies within &lt;1 kJ/mol of experiment can be achieved. Transition metal computational thermochemistry is fraught with more difficult electronic structure as well as much less high-quality experimental data with small uncertainties (necessary for benchmarking) in comparison to main group thermochemistry. In this work, using data from newer experimental methods including velocity map imaging and two-photon ionization spectroscopy as a guide, new ab initio methods for thermochemical prediction have been reevaluated and developed. More specifically, the correlation consistent composite approach (ccCA) for transition metals (ccCA-TM) has been reevaluated, and a higher accuracy extension of ccCA, called “super ccCA” (SccCA) is introduced. These methodologies have been applied to a series of vanadium species to demonstrate their utility.

Ab <i>initio</i> composite schemes for accurate transition metal compound thermochemistry

ACS Spring Meeting 2021

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Ab initio composite schemes for accurate transition metal compound thermochemistry