Open AccessExperimentally Established Benchmark Calculations of 31 P NMR Quantities
Author(s) -
Shenderovich Ilya G.
Publication year - 2021
Publication title -
chemistry ‐ methods
Language(s) - English
Resource type - Journals
ISSN - 2628-9725
DOI - 10.1002/cmtd.202000033
Subject(s) - electromagnetic shielding , basis (linear algebra) , basis set , intermolecular force , density functional theory , chemical shift , molecule , benchmark (surveying) , computational chemistry , chemistry , materials science , molecular physics , physics , mathematics , quantum mechanics , organic chemistry , geometry , geodesy , geography
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.