Getaway from the Geometry Factor Error in the Molecular Property Calculations: Efficient pecG-n (n = 1, 2) Basis Sets for the Geometry Optimization of Molecules Containing Light p Elements

The basis of all molecular property quantum chemical calculations is the correct equilibrium geometry. In this paper, new efficient pecG-n (n = 1, 2) basis sets for the geometry optimization of molecules containing hydrogen and p elements of 2–3 periods are proposed. These basis sets were optimized via the property-energy consistent (PEC) algorithm directed to the minimization of the molecular energy gradient relative to the bond lengths. New basis sets are compact and give equilibrium geometries of very high quality, which is comparable to that provided by considerably larger energy-optimized basis sets. The equilibrium geometries obtained with the pecG-n (n = 1, 2) basis sets and the other basis sets of diverse quality were tested in the CCSD calculations of different second-order molecular properties, including NMR shielding constants, static polarizabilities, and static magnetizabilities. As a result, new basis sets have demonstrated far superior performance as compared to the other energy-optimized basis sets of the same or close sizes commonly used at the geometry optimization stage.