The relativistic-pseudopotential correlation consistent Composite Approach (rp-ccCA) was used to determine the enthalpy of formation of 25 first row transition metal compounds and rp-ccCA-derived properties were compared to those previously obtained with an all-electron method composite method for transition metals (ccCA-TM). For the 3d metal systems, rp-ccCA achieves transition metal accuracy, i.e., within 3 kcal/mol of experimental data. By utilizing pseudopotentials within the rp-ccCA methodology, significant computational time savings are observed in comparison to all-electron basis sets and ccCA-TM. With the proven reliability and accuracy of rp-ccCA, the methodology was employed in order to construct a calibration set of 157 4d transition metal compounds and their enthalpies of formation in order to provide a large set of reliable energetics to be used in the development of future computational methodologies and as an aid for experimentalists in reaction design.

Application of a pseudopotential-based composite method for first and second row transition metal thermochemistry

247th National Meeting (2014)

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