Experimentally Established Benchmark Calculations of <sup>31</sup>P NMR Quantities
Ilya G. Shenderovich
Abstract
Abstract The accuracy of different density function theory functionals and the MP2 approximation in 31 P NMR calculations has been evaluated for ten phosphorous containing molecules in which the phosphorous atoms are not involved in intermolecular interactions. The obtained absolute chemical shielding tensors are compared to experimental ones. The dependence of the numerical values on the size of basis sets has been inspected from the 6‐311G(2d,p) to the pcSseg‐3 basis sets. General recommendations on the most reliable functionals and the smallest possible size of a basis set have been reported. For example, the use of the M06 L functional should be avoided. For five polycrystalline samples, the conformation of molecules has been identified with a high precision. These structures have been used to determine the reference values of the absolute chemical shielding for the TPSSh, B3LYP, and ωB97XD functionals and different basis sets. As reported in the supporting information, these structures can be used to determine the reference value of the absolute chemical shielding for any approximation of interest.