Quantitative prediction of gas-phase N15 and P31 nuclear magnetic shielding constants

Abstract

High-level ab initio benchmark calculations of the (15)N and (31)P NMR chemical shielding constants for a representative set of molecules are presented. The computations have been carried out at the Hartree-Fock self-consistent field (HF-SCF), density functional theory (DFT) (B-P86 and B3-LYP), second-order Moller-Plesset perturbation theory (MP2), coupled cluster singles and doubles (CCSD), and CCSD augmented by a perturbative treatment of triple excitations [CCSD(T)] level of theory using basis sets of triple zeta quality or better. The influence of the geometry, the treatment of electron correlation, as well as basis set and zero-point vibrational effects on the shielding constants are discussed and the results are compared to gas-phase experimental shifts. As for the first time a study using high-level post-HF methods is carried out for a second-row element, we also propose a family of basis sets suitable for the computation of (31)P shielding constants. The mean deviations observed for (15)N and (31)P are 0.9 [CCSD(T)/13s9p4d3f] and -3.3 ppm [CCSD(T)/15s12p4d3f2g], respectively, when corrected for zero-point vibrational effects. Results obtained at the DFT level of theory are of comparable accuracy to MP2 for (15)N and of comparable accuracy to HF-SCF for (31)P. However, they are not improved by inclusion of zero-point vibrational effects. The PN molecule is an especially interesting case with exceptionally large electron correlation effects on shielding constants beyond MP2 which, therefore, represents an excellent example for further benchmark studies.