Efficient Computation of Geometries for Gold Complexes

Computationally obtaining structural parameters along a reaction coordinate is commonly performed with Kohn-Sham density functional theory which generally provides a good balance between speed and accuracy. However, CPU times still range from inconvenient to prohibitive, depending on the size of the system under study. Herein, the tight binding GFN2-xTB method [C. Bannwarth, S. Ehlert, S. Grimme, J. Chem. Theory Comput. 2019 , 15 , 1652] is investigated as an alternative to produce reasonable geometries along a reaction path, i.e. reactant, product and transition state structures for a series of transformations involving gold complexes. A small mean error (1 kcal/mol) was found, with respect to an efficient composite hybrid-GGA exchange-correlation functional (PBEh-3c) paired with a double-zeta basis set, which is 2-3 orders of magnitude slower. The outlined protocol may serve as a rapid tool to probe the viability of proposed mechanistic pathways in the field of gold catalysis.