Comprehensive Benchmark Study on the Calculation of 29Si NMR Chemical Shifts

Abstract

A comprehensive and diverse benchmark set for the calculation of 29Si NMR chemical shifts is presented. The SiS146 set includes 100 silicon containing compounds with 146 experimentally determined reference 29Si NMR chemical shifts measured in nine different solvents in a range from -400 to +828 ppm. Silicon atoms bound to main group elements as well as transition metals with coordination numbers of 2-6 in various bonding patterns including multiple bonds and coordinative and aromatic bonding are represented. The performance of various common and specialized density functional approximations including (meta-)GGA, hybrid, and double-hybrid functionals in combination with different AO basis sets and for differently optimized geometries is evaluated. The role of scalar-relativistic effects is further investigated by inclusion of the zeroth order regular approximation (ZORA) method into the calculations. GGA density functional approximations (DFAs) are found to outperform hybrid DFAs with B97-D3 performing best with an MAD of 7.2 ppm for the subset including only light atoms (Z < 18), while TPSSh is the best tested hybrid functional with an MAD of 10.3 ppm. For 29Si cores in the vicinity of heavier atoms, the application of ZORA proved indispensable. Inclusion of spin-orbit effects into the 29Si NMR chemical shift calculation decreases the mean absolute deviations by up to 74% compared to calculations applying effective core potentials.